JP2008277004A - Non-aqueous electrolytic solution for secondary battery and non-aqueous electrolytic solution secondary battery using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-aqueous electrolytic solution for a secondary battery that is excellent in cycle characteristics, storage characteristics, gas occurrence suppression during continuous charging, and battery characteristics, and a non-aqueous electrolytic solution secondary battery using the same. <P>SOLUTION: The non-aqueous electrolytic solution is mainly composed of an electrolyte and a non-aqueous solvent dissolving the electrolyte. The non-aqueous electrolytic solution includes a monofluorophosphoric acid salt and/or a difluorophosphoric acid salt. The non-aqueous electrolytic solution further includes at least one kind of compound selected from a group consisting of a compound expressed by general formula (1), a nitrile compound, an isocyanate compound, a phosphazene compound, a disulfonic acid ester compound, a sulfide compound, a disulfide compound, an acid anhydride, a lactone compound having a substituent group at an α-position, and a compound having a carbon-carbon triple bond. Here, in general formula (1), R<SP>1</SP>, R<SP>2</SP>, and R<SP>3</SP>represent each independently a fluorine atom, a 1-12C alkyl group that may be replaced by a fluorine atom, or a 1-12C alkoxy group that may be replaced by a fluorine atom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte for a secondary battery and a non-aqueous electrolyte secondary battery using the same, and more specifically, a non-aqueous electrolyte for a lithium secondary battery containing a specific component. And a non-aqueous electrolyte secondary battery using the same.

  In recent years, with the miniaturization of electronic devices, the demand for higher capacity for secondary batteries has increased, and lithium secondary batteries with higher energy density than nickel-cadmium batteries and nickel-hydrogen batteries have attracted attention. Yes.

As an electrolyte of the lithium secondary battery, an electrolyte such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , LiCF ₃ (CF ₂ ) ₃ SO ₃ , Cyclic carbonates such as ethylene carbonate and propylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; cyclic esters such as γ-butyrolactone and γ-valerolactone; chain carboxyls such as methyl acetate and methyl propionate Non-aqueous electrolytes dissolved in non-aqueous solvents such as acid esters are used.

  In order to improve battery characteristics such as load characteristics, cycle characteristics, and storage characteristics of such lithium secondary batteries, various studies have been made on non-aqueous solvents and electrolytes. For example, in Patent Document 1, by using an electrolyte containing a phosphinic acid ester, it is possible to produce a battery in which deterioration of battery performance during continuous charging is suppressed during high-temperature storage. By using an electrolytic solution to which an organic compound having two or more cyano groups is added, a secondary battery excellent in charge / discharge cycle life at a voltage exceeding 4.2 V has been proposed.

  In particular, in a continuous charge state in which a weak current is always supplied to keep the battery self-discharged and kept in a charged state, the electrode activity is always high, so the battery capacity deterioration is promoted or the electrolyte is decomposed. Due to this, gas is likely to be generated. In particular, in a high-capacity battery, since the space volume inside the battery is small, there is a problem that even if a small amount of gas is generated due to decomposition of the electrolytic solution, the internal pressure of the battery increases remarkably. As continuous charging characteristics, not only is there little capacity degradation, but there is a strong demand for suppressing gas generation.

However, the electrolytic solution containing the compounds described in Patent Document 1 and Patent Document 2 has a certain effect in improving cycle characteristics and storage characteristics, but it suppresses gas generation during continuous charging and deterioration of battery characteristics. Was not enough
JP 2004-363077 A JP-A-7-176322

  The present invention has been made in view of the above-described background art, and an object thereof is to provide a non-aqueous electrolyte for a secondary battery excellent in cycle characteristics, storage characteristics, suppression of gas generation during continuous charging, and battery characteristics.

  As a result of intensive studies in view of the above-mentioned problems, the present inventor further added a compound represented by the general formula (1), a nitrile compound, to a nonaqueous electrolytic solution containing a monofluorophosphate and / or a difluorophosphate. , An isocyanate compound, a phosphazene compound, a disulfonic acid ester compound, a sulfide compound, a disulfide compound, an acid anhydride, a lactone compound having a substituent at the α-position, and a compound having a carbon-carbon triple bond It was found that when the above compound was added, gas generation suppression during continuous charging and battery characteristics could be maintained well, and the present invention was completed.

［一般式（１）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、フッ素原子、フッ素原子で置換されていてもよい炭素数１〜１２のアルキル基、又は、フッ素原子で置換されていてもよい炭素数１〜１２のアルコキシ基を表す。］ That is, the present invention is a non-aqueous electrolyte mainly composed of an electrolyte and a non-aqueous solvent that dissolves the electrolyte, and contains a monofluorophosphate and / or a difluorophosphate, and is further represented by the general formula (1). From the group consisting of compounds, nitrile compounds, isocyanate compounds, phosphazene compounds, disulfonic acid ester compounds, sulfide compounds, disulfide compounds, acid anhydrides, lactone compounds having a substituent at the α-position, and compounds having a carbon-carbon triple bond The present invention provides a non-aqueous electrolyte containing at least one selected compound (hereinafter sometimes abbreviated as “the compound of the present invention”).

[In General Formula (1), R ¹ , R ² and R ³ are each independently substituted with a fluorine atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. The C1-C12 alkoxy group which may be represented. ]

  The present invention also provides a non-aqueous electrolyte secondary battery comprising at least a negative electrode and a positive electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte described above. The present invention provides a non-aqueous electrolyte secondary battery that is an electrolyte.

  According to the present invention, it is possible to provide a non-aqueous electrolyte solution and a non-aqueous electrolyte secondary battery excellent in cycle characteristics, storage characteristics, gas generation suppression during continuous charging, and battery characteristics.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is limited to these specific contents. However, various modifications can be made within the scope of the gist.

[1. Non-aqueous electrolyte]
The non-aqueous electrolyte solution of the present invention is a non-aqueous electrolyte solution mainly composed of an electrolyte and a non-aqueous solvent that dissolves the electrolyte. The non-aqueous electrolyte solution contains a monofluorophosphate and / or a difluorophosphate. 1) a compound represented by 1), a nitrile compound, an isocyanate compound, a phosphazene compound, a disulfonic acid ester compound, a sulfide compound, a disulfide compound, an acid anhydride, a lactone compound having a substituent at the α-position, and a compound having a carbon-carbon triple bond At least one compound selected from the group consisting of:

<1-1. Electrolyte>
The non-aqueous electrolyte solution of the present invention contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte. There is no restriction | limiting in the electrolyte used for the non-aqueous electrolyte of this invention, The well-known thing used as an electrolyte can be arbitrarily employ | adopted and contained in the target non-aqueous electrolyte secondary battery. When the non-aqueous electrolyte of the present invention is used for a non-aqueous electrolyte secondary battery, the electrolyte is preferably a lithium salt.

As a specific example of the electrolyte, for example,
LiClO ₄ ,
LiAsF ₆ ,
LiPF ₆ ,
Li ₂ CO ₃ ,
Inorganic lithium salts such as LiBF ₄ ;

LiCF ₃ SO ₃ ,
LiN (CF ₃ SO ₂ ) ₂ ,
LiN (C ₂ F ₅ SO ₂ ) ₂ ,
LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ),
LiC (CF ₃ SO ₂ ) ₃ ,
LiPF ₄ (CF ₃ ) ₂ ,
LiPF ₄ (C ₂ F ₅ ) ₂ ,
LiPF ₄ (CF ₃ SO ₂ ) ₂ ,
LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ ,
LiBF ₃ (CF ₃ ),
LiBF ₃ (C ₂ F ₅ ),
LiBF ₂ (CF ₃ ) ₂ ,
LiBF ₂ (C ₂ F ₅ ) ₂ ,
LiBF ₂ (CF ₃ SO ₂ ) ₂ ,
Fluorine-containing organic lithium salts such as LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ ;

Lithium bis (oxalato) borate,
Lithium tris (oxalato) phosphate,
Dicarboxylic acid complex lithium salts such as lithium difluorooxalatoborate;

KPF ₆ ,
NaPF ₆ ,
NaBF ₄ ,
Sodium salt or potassium salt such as CF ₃ SO ₃ Na;
Etc.

Of these, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ or lithium bis (oxalato) borate are preferred, and LiPF ₆ or LiBF ₄ is preferred. Particularly preferred.

  One type of electrolyte may be used alone, or two or more types of electrolytes may be used in any combination and ratio. Among these, it is preferable to use two kinds of specific inorganic lithium salts in combination or to use inorganic lithium salts and fluorine-containing organic lithium salts in combination since deterioration after high-temperature storage is suppressed.

In particular, the combination and the LiPF ₆ and LiBF _4, and an inorganic lithium salt such as _{LiPF 6, LiBF 4, LiCF 3} SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) _2, etc. It is preferable to use in combination with a fluorine-containing organic lithium salt.

Furthermore, when LiPF ₆ and LiBF ₄ are used in combination, it is preferable that LiBF ₄ is contained at a ratio of usually 0.01% by mass or more and usually 20% by mass or less with respect to the entire electrolyte. LiBF ₄ has a low degree of dissociation, and if the ratio is too high, the resistance of the non-aqueous electrolyte may be increased.

On the other hand, when inorganic lithium salts such as LiPF ₆ and LiBF ₄ are used in combination with fluorine-containing organic lithium salts such as LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , and LiN (C ₂ F ₅ SO ₂ ) ₂ The proportion of the inorganic lithium salt in the entire lithium salt is preferably in the range of 70% by mass to 99% by mass. In general, fluorine-containing organic lithium salts have a higher molecular weight than inorganic lithium salts, and if the content ratio is too high, the ratio of the non-aqueous solvent to the entire non-aqueous electrolyte may decrease and the resistance of the non-aqueous electrolyte may increase. is there.

  Further, the concentration of the lithium salt in the final composition of the non-aqueous electrolyte of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 0.5 mol / L or more, preferably 0.6 mol / L L or more, more preferably 0.8 mol / L or more, and usually 3 mol / L or less, preferably 2 mol / L or less, more preferably 1.5 mol / L or less. If this concentration is too low, the electrical conductivity of the non-aqueous electrolyte may be insufficient. If the concentration is too high, the electrical conductivity will decrease due to an increase in viscosity, and the non-aqueous electrolyte of the present invention will be used. The performance of the non-aqueous electrolyte secondary battery may deteriorate

In particular, when the non-aqueous solvent of the non-aqueous electrolyte is mainly composed of a carbonate compound such as alkylene carbonate or dialkyl carbonate, LiPF ₆ may be used alone, but when used together with LiBF ₄ , capacity deterioration due to continuous charging is suppressed. This is preferable. When these are used in combination, the molar ratio of LiBF _{4 to} LiPF ₆ is usually 0.005 or more, preferably 0.01 or more, particularly preferably 0.05 or more, and usually 0.4 or less, preferably 0.2. It is as follows. If this molar ratio is too large, the battery characteristics after high-temperature storage tend to be lowered. Conversely, if it is too small, it is difficult to obtain the effect of suppressing capacity deterioration during continuous charging.

When the non-aqueous solvent of the non-aqueous electrolyte contains 50% by volume or more of a cyclic carboxylic acid ester compound such as γ-butyrolactone or γ-valerolactone, LiBF ₄ represents 50% by mole or more of the total lithium salt. It is preferable to occupy.

<1-2. Compound of the present invention>
The non-aqueous electrolyte solution of the present invention contains the “compound of the present invention”. The “compound of the present invention” is a compound represented by the general formula (1), a nitrile compound, an isocyanate compound, a phosphazene compound, a disulfonic acid ester compound, a sulfide compound, a disulfide compound, an acid anhydride, and a substituent at the α-position. A lactone compound or a compound having a carbon-carbon triple bond. Hereinafter, the compounds constituting the “compound of the present invention” group in the present invention will be described more specifically.

［一般式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、フッ素原子、フッ素原子で置換されていてもよい炭素数１〜１２のアルキル基、又は、フッ素原子で置換されていてもよい炭素数１〜１２のアルコキシ基を表す。］ <1-2-1. Compound represented by general formula (1)>

[In General Formula (1), R ¹ , R ² and R ³ are each independently substituted with a fluorine atom, a C 1-12 alkyl group which may be substituted with a fluorine atom, or a fluorine atom. Represents an optionally substituted alkoxy group having 1 to 12 carbon atoms. ]

  Although it does not specifically limit as a C1-C12 alkyl group, Preferably it is C1-C8, Most preferably, a 1-6 chain or cyclic alkyl group is mentioned. Of these, a chain alkyl group is preferred. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, cyclohexyl Etc.

  The alkoxy group having 1 to 12 carbon atoms is not particularly limited, but is preferably an alkoxy group having 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group.

  Specific examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group.

  Specific examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a trifluoroethoxy group, a pentafluoroethoxy group, and the like.

Specific examples of the compound in which all of R ¹ , R ² and R ³ are alkoxy groups include, for example,
Trimethyl phosphate,
Ethyl dimethyl phosphate,
Dimethyl n-propyl phosphate,
N-butyldimethyl phosphate,
Diethyl methyl phosphate,
Ethyl n-propylmethyl phosphate,
N-butylethylmethyl phosphate,
Di-n-propylmethyl phosphate,
N-butyl n-propylmethyl phosphate,
Di-n-butylmethyl phosphate,
Triethyl phosphate,
Diethyl n-propyl phosphate,
N-butyldiethyl phosphate,
Di-n-propylethyl phosphate,
N-butyl n-propylethyl phosphate,
Di-n-butylethyl phosphate,
Tri-n-propyl phosphate,
N-butyl di-n-propyl phosphate,
Di-n-butyl phosphate n-propyl phosphate,
Tri-n-butyl phosphate,
Cyclopentyldimethyl phosphate,
Cyclopentyl diethyl phosphate,
Cyclopentyl di-n-propyl phosphate,
Cyclopentyl di-n-butyl phosphate,
Cyclopentylethyl methyl phosphate,
Dicyclopentylmethyl phosphate,
Tricyclopentyl phosphate,
Cyclohexyldimethyl phosphate,
Cyclohexyl diethyl phosphate,
Cyclohexyldi-n-propyl phosphate,
Cyclohexyldi-n-butyl phosphate,
Cyclohexylethyl methyl phosphate,
Dicyclohexylmethyl phosphate,
Tricyclohexyl phosphate,
Dimethyl trifluoromethyl phosphate,
Diethyl trifluoromethyl phosphate,
Ethyl methyl trifluoromethyl phosphate,
Phosphoric acid (2,2,2-trifluoroethyl) diethyl dimethyl phosphate (2,2,2-trifluoroethyl)
Ethyl phosphate (2,2,2-trifluoroethyl) methyl,
Phosphoric acid (pentafluoroethyl) dimethyl phosphate (pentafluoroethyl)
Ethyl bis (trifluoromethyl) methyl phosphate (pentafluoroethyl) methyl phosphate,
Tris phosphate (trifluoromethyl),
Bis (2,2,2-trifluoroethyl) methyl phosphate,
Bis (2,2,2-trifluoroethyl) trifluoromethyl phosphate,
Bis (pentafluoroethyl) methyl phosphate,
Bis (pentafluoroethyl) trifluoromethyl phosphate,
Bis (trifluoromethyl) ethyl phosphate,
Bis (trifluoromethyl) -2,2,2-trifluoroethyl phosphate,
Bis (trifluoromethyl) pentafluoroethyl phosphate,
Bis (2,2,2-trifluoroethyl) ethyl phosphate,
Tris phosphate (2,2,2-trifluoroethyl),
Bis (2,2,2-trifluoroethyl) pentafluoroethyl phosphate,
Bis (pentafluoroethyl) ethyl phosphate,
Bis (pentafluoroethyl) phosphate-2,2,2-trifluoroethyl phosphate,
Examples thereof include tris phosphate (pentafluoroethyl).

Among the phosphoric acid esters exemplified above,
Trimethyl phosphate,
Ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate, dimethyl trifluoromethyl phosphate,
Diethyl trifluoromethyl phosphate,
Ethyl methyl trifluoromethyl phosphate,
Phosphoric acid (2,2,2-trifluoroethyl) diethyl dimethyl phosphate (2,2,2-trifluoroethyl)
Ethyl phosphate (2,2,2-trifluoroethyl) methyl,
Phosphoric acid (pentafluoroethyl) dimethyl phosphate (pentafluoroethyl)
Ethyl phosphate (pentafluoroethyl) methyl

Bis (trifluoromethyl) methyl phosphate,
Tris phosphate (trifluoromethyl),
Bis (2,2,2-trifluoroethyl) methyl phosphate,
Bis (2,2,2-trifluoroethyl) trifluoromethyl phosphate,
Bis (pentafluoroethyl) methyl phosphate,
Bis (pentafluoroethyl) trifluoromethyl phosphate,
Bis (trifluoromethyl) ethyl phosphate,
Bis (trifluoromethyl) -2,2,2-trifluoroethyl phosphate,
Bis (trifluoromethyl) pentafluoroethyl phosphate,
Bis (2,2,2-trifluoroethyl) ethyl phosphate,
Tris phosphate (2,2,2-trifluoroethyl),
Bis (2,2,2-trifluoroethyl) pentafluoroethyl phosphate,
Bis (pentafluoroethyl) ethyl phosphate,
Bis (pentafluoroethyl) phosphate-2,2,2-trifluoroethyl phosphate,
Tris phosphate (pentafluoroethyl) and the like are preferable.

Specific examples of the compound in which any one of R ¹ , R ² and R ³ is an alkyl group and any two are alkoxy groups include, for example,
Dimethyl methylphosphonate,
Diethyl ethylphosphonate,
n-propyl phosphonate di-n-propyl,
Diisopropyl isopropylphosphonate,
di-n-butyl n-butylphosphonate,
Diisobutyl isobutylphosphonate,
di-tert-butyl tert-butylphosphonate,
Dicyclopentyl cyclopentylphosphonate,
Cyclohexyl phosphonate dicyclohexyl,
Diethyl methylphosphonate,
Di-n-propyl methylphosphonate,
Di-n-butyl methylphosphonate,
Dicyclopentyl methylphosphonate,
Dicyclohexyl methylphosphonate,
Dimethyl ethylphosphonate,
Di-n-propyl ethylphosphonate,
Di-n-butyl ethylphosphonate,
Dicyclopentyl ethylphosphonate,
Dicyclohexyl ethylphosphonate,
dimethyl n-propylphosphonate,
diethyl n-propylphosphonate,
dimethyl n-butylphosphonate,
diethyl n-butylphosphonate,
Dimethyl cyclohexylphosphonate,
Diethyl cyclohexylphosphonate,
Ethyl methyl phosphonate,
Methyl n-propyl methylphosphonate,
N-butylmethyl methylphosphonate,
Cyclopentylmethyl methylphosphonate,
Cyclohexylmethyl methylphosphonate,
Ethyl n-propyl methylphosphonate,
Cyclohexylethyl methylphosphonate,
Ethyl methyl ethylphosphonate,
Methyl n-propyl ethylphosphonate,
N-butylmethyl ethylphosphonate,
Cyclopentylmethyl ethylphosphonate,
Cyclohexylmethyl ethylphosphonate,
Ethyl n-propyl ethylphosphonate,
Cyclohexylethyl ethylphosphonate,
ethyl methyl n-propylphosphonate,
n-propyl methyl n-propylphosphonate,
n-butylmethyl n-propylphosphonate,
cyclopentylmethyl n-propylphosphonate,
cyclohexylmethyl n-propylphosphonate,
n-propyl ethyl n-propylphosphonate,
cyclohexylethyl n-propylphosphonate n-butylethylmethylphosphonate,
n-propyl methyl n-butylphosphonate,
n-butylmethyl n-butylphosphonate,
cyclopentylmethyl n-butylphosphonate,
cyclohexylmethyl n-butylphosphonate,
n-butyl ethyl n-butylphosphonate,
cyclohexylethyl n-butylphosphonate,
Ethyl methyl cyclohexylphosphonate,
Methyl n-propyl cyclohexylphosphonate,
N-butylmethyl cyclohexylphosphonate,
Cyclopentylmethyl cyclohexylphosphonate,
Cyclohexylmethyl cyclohexylphosphonate,
Ethyl n-propyl cyclohexylphosphonate,
Cyclohexylethyl cyclohexylphosphonate,
Diperfluoromethyl methylphosphonate,
Di (2,2,2-trifluoroethyl) methylphosphonate,
Diperfluoroethyl methylphosphonate,
Methylphosphonate di (2-fluorocyclohexyl),
Methylphosphonate di (3-fluorocyclohexyl),
Methylphosphonate di (4-fluorocyclohexyl),
Diperfluoromethyl ethylphosphonate,
Di (2,2,2-trifluoroethyl) ethylphosphonate,
Diperfluoroethyl ethylphosphonate,
Di (2-fluorocyclohexyl) ethylphosphonate,
Di (3-fluorocyclohexyl) ethylphosphonate,
Di (4-fluorocyclohexyl) ethylphosphonate,
n-propylphosphonic acid di (2,2,2-trifluoroethyl),
diperfluoroethyl n-propylphosphonate,
n-butylphosphonate di (2,2,2-trifluoroethyl),
diperfluoroethyl n-butylphosphonate,
Cyclohexylphosphonic acid di (2,2,2-trifluoroethyl),
Diperfluoroethyl cyclohexylphosphonate,
Methyl perfluoromethyl methylphosphonate,
Methyl methylphosphonate (2,2,2-trifluoroethyl),
Methyl perfluoroethyl methylphosphonate,
Methyl (2-fluorocyclohexyl) methylphosphonate,
Methyl (3-fluorocyclohexyl) methylphosphonate,
Methyl (4-fluorocyclohexyl) methylphosphonate,
Ethyl perfluoroethyl methylphosphonate,
Cyclohexyl methylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl methylphosphonate,
Perfluoroethyl methylphosphonate (2,2,2-trifluoroethyl),
Ethyl ethylphosphonate (2,2,2-trifluoroethyl),
Ethyl perfluoroethyl ethylphosphonate,
Cyclohexyl ethylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl ethylphosphonate,
Perfluoroethyl ethylphosphonate (2,2,2-trifluoroethyl),
Ethylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
ethyl n-propylphosphonate (2,2,2-trifluoroethyl),
n-propylphosphonic acid ethyl perfluoroethyl,
cyclohexyl n-propylphosphonate (2,2,2-trifluoroethyl),
cyclohexyl perfluoroethyl n-propylphosphonate,
perfluoroethyl n-propylphosphonate (2,2,2-trifluoroethyl),
n-propylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
ethyl n-butylphosphonate (2,2,2-trifluoroethyl),
n-butyl ethyl phosphonate perfluoroethyl;
cyclohexyl n-butylphosphonate (2,2,2-trifluoroethyl),
cyclohexyl perfluoroethyl n-butylphosphonate,
perfluoroethyl n-butylphosphonate (2,2,2-trifluoroethyl),
n-butylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
Ethyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl ethyl phosphonate perfluoroethyl,
Cyclohexyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl cyclohexylphosphonate,
Perfluoroethyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
Perfluoromethylphosphonate diperfluoromethyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2,2,2-trifluoroethyl),
Perfluoroethyl phosphonate diperfluoroethyl,
(2-fluorocyclohexyl) phosphonic acid di (2-fluorocyclohexyl),
(3-fluorocyclohexyl) phosphonic acid di (3-fluorocyclohexyl),
(4-fluorocyclohexyl) phosphonic acid di (4-fluorocyclohexyl),
Dimethyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) diethyl phosphonate,
Di-n-butyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) phosphonic acid dicyclohexyl,
(2,2,2-trifluoroethyl) phosphoric acid diperfluoroethyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2-fluorocyclohexyl),
(2,2,2-trifluoroethyl) ethyl methylphosphonate,
N-butylmethyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) cyclohexylmethyl phosphonate,
Methyl (2,2,2-trifluoroethyl) phosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) methyl perfluoroethyl phosphonate,
(2,2,2-trifluoroethyl) phosphonic acid (2-fluorocyclohexyl) methyl,
(2,2,2-trifluoroethyl) cyclohexylethyl phosphonate,
(2,2,2-trifluoroethyl) ethyl phosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phosphonic acid cyclohexyl (2,2,2-trifluoroethyl),
(2-fluorocyclohexyl) dimethyl phosphonate,
(2-fluorocyclohexyl) diethyl phosphonate,
(2-fluorocyclohexyl) phosphoric acid dicyclohexyl,
(2-fluorocyclohexyl) phosphonic acid bis (2,2,2-trifluoroethyl),
(2-fluorocyclohexyl) ethyl methylphosphonate,
(2-fluorocyclohexyl) cyclohexylmethyl phosphonate,
(2-Fluorocyclohexyl) methyl phosphonate (2,2,2-trifluoroethyl)
Etc.

Among the phosphonates exemplified above,
Dimethyl methylphosphonate,
Diethyl ethylphosphonate,
n-propyl phosphonate di-n-propyl,
di-n-butyl n-butylphosphonate,
Diisobutyl isobutylphosphonate,
Diethyl methylphosphonate,
Di-n-butyl methylphosphonate,
Dimethyl ethylphosphonate,
Di-n-propyl ethylphosphonate,
dimethyl n-propylphosphonate,
diethyl n-propylphosphonate,
Di (2,2,2-trifluoroethyl) methylphosphonate,
Di (2,2,2-trifluoroethyl) ethylphosphonate,
Perfluoromethylphosphonate diperfluoromethyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2,2,2-trifluoroethyl),
Perfluoroethyl phosphonate diperfluoroethyl,
Dimethyl (2,2,2-trifluoroethyl) phosphonate,
Preference is given to diethyl (2,2,2-trifluoroethyl) phosphonate and the like.

Specific examples of the compound in which any ^{two of} R ¹ , R ² and R ³ are alkyl groups and any one is an alkoxy group include, for example,
Methyl dimethylphosphinate,
Ethyl diethylphosphinate,
N-propyl di-n-propylphosphinate,
Isopropyl diisopropylphosphinate,
N-butyl di-n-butylphosphinate,
Isobutyl diisobutylphosphinate,
Tert-butyl ditert-butylphosphinate,
Cyclopentyl dicyclopentylphosphinate,
Cyclohexyl dicyclohexylphosphinate,
Methyl diethylphosphinate,
Methyl n-propylphosphinate,
Methyl diisopropylphosphinate,
Methyl n-butylphosphinate,
Methyl diisobutylphosphinate,
Methyl tert-butylphosphinate,
Methyl dicyclopentylphosphinate,
Methyl dicyclohexylphosphinate,
Ethyl dimethylphosphinate,
Ethyl di-n-propylphosphinate,
Ethyl diisopropylphosphinate,
Ethyl di-n-butylphosphinate,
Ethyl diisobutylphosphinate,
Ethyl ditert-butylphosphinate,
Ethyl dicyclopentylphosphinate,
Ethyl dicyclohexylphosphinate,
N-propyl dimethylphosphinate,
N-propyl diethylphosphinate,
N-propyl diisopropylphosphinate,
N-propyl di-n-butylphosphinate,
N-propyl diisobutylphosphinate,
N-propyl ditert-butylphosphinate,
N-propyl dicyclopentylphosphinate,
N-propyl dicyclohexylphosphinate,
N-butyl dimethylphosphinate,
N-butyl diethylphosphinate,
N-butyl dicyclohexylphosphinate,
Cyclohexyl dimethylphosphinate,
Cyclohexyl diethylphosphinate,
Cyclohexyl di-n-propylphosphinate,
Cyclohexyl di-n-butylphosphinate,
Ethyl methylmethylphosphinate,
Methyl n-propylphosphinate methyl,
methyl n-butylmethylphosphinate,
Methyl cyclohexylmethylphosphinate,
Methyl n-propylphosphinate methyl n-butylethylphosphinate,
Methyl cyclohexylethylphosphinate,
Cyclohexyl n-propyphosphinic acid methyl ester,
methyl n-butylcyclohexylphosphinate,
Ethyl ethyl phosphinate,
Methyl n-propylphosphinate,
ethyl n-butylmethylphosphinate,
Ethyl cyclohexylmethylphosphinate,
n-butylethyl ethylphosphinate,
Cyclohexyl ethyl phosphinate,
n-butylcyclohexyl ethyl phosphinate,
N-butyl ethylmethylphosphinate,
N-butyl methyl n-butylphosphinate,
N-butyl cyclohexylmethylphosphinate,
N-butyl methylphenylphosphinate,
n-butyl n-butylethylphosphinate,
N-butyl cyclohexylethylphosphinate,
N-butyl ethylphenylphosphinate,
n-butylcyclohexylphosphinate n-butyl,
N-butyl cyclohexylvinylphosphinate,
Cyclohexyl ethyl methylphosphinate,
Cyclohexyl methyl n-butylphosphinate,
Cyclohexylmethylphosphinic acid cyclohexyl,
cyclohexyl n-butylethylphosphinate,
Cyclohexyl ethyl phosphinate cyclohexyl,
n-butylcyclohexyl phosphinic acid cyclohexyl,
Perfluoromethyl bisperfluoromethylphosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Perfluoroethyl bisperfluoroethylphosphinate,
Di (2-fluorocyclohexyl) phosphinic acid (2-fluorocyclohexyl),
Di (3-fluorocyclohexyl) phosphinic acid (3-fluorocyclohexyl),
Di (4-fluorocyclohexyl) phosphinic acid (4-fluorocyclohexyl),
Methyl bisperfluoromethylphosphinate,
Methyl bis (2,2,2-trifluoroethyl) phosphinate,
Methyl bisperfluoroethylphosphinate,
Methyl di (2-fluorocyclohexyl) phosphinate,
Methyl di (3-fluorocyclohexyl) phosphinate,
Methyl di (4-fluorocyclohexyl) phosphinate,
Ethyl bisperfluoromethylphosphinate,
Ethyl bis (2,2,2-trifluoroethyl) phosphinate,
Ethyl bisperfluoroethylphosphinate,
Ethyl di (2-fluorocyclohexyl) phosphinate,
Ethyl di (3-fluorocyclohexyl) phosphinate,
Ethyl di (4-fluorocyclohexyl) phosphinate,
N-butyl bis (2,2,2-trifluoroethyl) phosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
Dimethylphosphinic acid (2,2,2-trifluoroethyl),
Diethylphosphinic acid (2,2,2-trifluoroethyl),
Di-n-butylphosphinic acid (2,2,2-trifluoroethyl),
Dicyclohexylphosphinic acid (2,2,2-trifluoroethyl),
Methyl (2,2,2-trifluoroethyl) ethyl phosphinate,
Ethyl methyl (2-fluorophenyl) phosphinate,
Ethyl (2,2,2-trifluoroethyl) phosphinate,
n-butyl (2,2,2-trifluoroethyl) ethyl phosphinate,
Cyclohexyl (2,2,2-trifluoroethyl) ethyl phosphinate,
N-butyl methyl (2,2,2-trifluoroethyl) phosphinate,
N-butyl ethyl (2,2,2-trifluoroethyl) phosphinate,
n-butyl n-butyl (2,2,2-trifluoroethyl) phosphinate,
N-butyl cyclohexyl (2,2,2-trifluoroethyl) phosphinate,
Cyclohexyl methyl (2,2,2-trifluoroethyl) phosphinate,
Cyclohexyl ethyl (2,2,2-trifluoroethyl) phosphinate,
n-butyl (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
Cyclohexyl (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
Ethylmethylphosphinic acid (2,2,2-trifluoroethyl),
Methyl n-butylphosphinic acid (2,2,2-trifluoroethyl),
Cyclohexylmethylphosphinic acid (2,2,2-trifluoroethyl),
Methyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
n-butylethylphosphinic acid (2,2,2-trifluoroethyl),
Cyclohexylethylphosphinic acid (2,2,2-trifluoroethyl),
Ethyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
n-butylcyclohexylphosphinic acid (2,2,2-trifluoroethyl),
n-butyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Cyclohexyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phenylphosphinic acid (2,2,2-trifluoroethyl) and the like.

Among the phosphinic acid esters exemplified above,
Methyl dimethylphosphinate,
Ethyl diethylphosphinate,
N-propyl di-n-propylphosphinate,
N-butyl di-n-butylphosphinate,
Methyl diethylphosphinate,
Ethyl dimethylphosphinate,
Perfluoromethyl bisperfluoromethylphosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Perfluoroethyl bisperfluoroethylphosphinate,
Methyl bisperfluoromethylphosphinate,
Methyl bis (2,2,2-trifluoroethyl) phosphinate,
Methyl bisperfluoroethylphosphinate,
Ethyl bisperfluoromethylphosphinate,
Ethyl bis (2,2,2-trifluoroethyl) phosphinate,
Ethyl bisperfluoroethylphosphinate,
Dimethylphosphinic acid (2,2,2-trifluoroethyl),
Diethylphosphinic acid (2,2,2-trifluoroethyl) and the like are preferable.

Specific examples of the compound in which all of R ¹ , R ² and R ³ are alkyl groups include
Trimethylphosphine oxide,
Triethylphosphine oxide,
Tri-n-propylphosphine oxide,
Triisopropylphosphine oxide,
Tri-n-butylphosphine oxide,
Triisobutylphosphine oxide,
Tri-tert-butylphosphine oxide,
Tricyclopentylphosphine oxide,
Tricyclohexylphosphine oxide,
Ethyldimethylphosphine oxide,
Dimethyl n-propylphosphine oxide,
Isopropyldimethylphosphine oxide,
n-butyldimethylphosphine oxide,
Isobutyldimethylphosphine oxide,
tert-butyldimethylphosphine oxide,
Cyclopentyldimethylphosphine oxide,
Cyclohexyldimethylphosphine oxide,
Diethylmethylphosphine oxide,
Diethyl n-propylphosphine oxide,
Diethyl n-butylphosphine oxide,
Cyclohexyl diethyl phosphine oxide,
Methyldi n-propylphosphine oxide,
Ethyldi-n-propylphosphine oxide,
Cyclohexyldi n-propylphosphine oxide,
Di-n-butylmethylphosphine oxide,
Di-n-butylethylphosphine oxide,
Di-n-butylcyclohexylphosphine oxide,
Dicyclohexylmethylphosphine oxide,
Dicyclohexylethylphosphine oxide,
Dicyclohexyl n-propylphosphine oxide,
n-butyldicyclohexylphosphine oxide,
Ethylmethyl n-propylphosphine oxide,
Ethylmethylisopropylphosphine oxide,
Ethylmethyl n-butylphosphine oxide,
Ethyl methyl isobutyl phosphine oxide,
Ethylmethyl tert-butylphosphine oxide,
Ethylmethylcyclopentylphosphine oxide,
Ethylmethylcyclohexylphosphine oxide,
n-butylmethyl n-propylphosphine oxide,
n-butylmethylcyclohexylphosphine oxide,
Cyclohexylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
Triperfluoromethylphosphine oxide,
Tri (2,2,2-trifluoroethyl) phosphine oxide,
Triperfluoroethylphosphine oxide,
Tri (2-fluorocyclohexyl) phosphine oxide,
Tri (3-fluorocyclohexyl) phosphine oxide,
Tri (4-fluorocyclohexyl) phosphine oxide,
Perfluoromethyldimethylphosphine oxide,
(2,2,2-trifluoroethyl) dimethylphosphine oxide,
Perfluoroethyldimethylphosphine oxide,
(2-fluorocyclohexyl) dimethylphosphine oxide,
(3-fluorocyclohexyl) dimethylphosphine oxide,
(4-fluorocyclohexyl) dimethylphosphine oxide,
Diethyl (2,2,2-trifluoroethyl) phosphine oxide,
Di-n-butyl (2,2,2-trifluoroethyl) phosphine oxide,
Dicyclohexyl (2,2,2-trifluoroethyl) phosphine oxide,
Di (2,2,2-trifluoroethyl) methylphosphine oxide,
Ethyl (2,2,2-trifluoroethyl) phosphine oxide,
n-butyldi (2,2,2-trifluoroethyl) phosphine oxide,
Cyclohexyldi (2,2,2-trifluoroethyl) phosphine oxide,
Ethylmethylperfluoromethylphosphine oxide,
Ethylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
Ethylmethylperfluoroethylphosphine oxide,
Ethylmethyl (2-fluorocyclohexyl) phosphine oxide,
Ethylmethyl (3-fluorocyclohexyl) phosphine oxide,
Ethylmethyl (4-fluorocyclohexyl) phosphine oxide,
n-butylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
n-butylethyl n-propylphosphine oxide,
n-butylethylcyclohexylphosphine oxide,
n-butylethyl (2,2,2-trifluoroethyl) phosphine oxide,
Cyclohexylethyl (2,2,2-trifluoroethyl) phosphine oxide,
and n-butylcyclohexyl (2,2,2-trifluoroethyl) phosphine oxide.

Among the phosphine oxides exemplified above,
Trimethylphosphine oxide,
Triethylphosphine oxide,
Tri-n-propylphosphine oxide,
Tri-n-butylphosphine oxide,
Ethyldimethylphosphine oxide,
Diethylmethylphosphine oxide,
Tripperfluoromethylphosphine oxide tri (2,2,2-trifluoroethyl) phosphine oxide,
Triperfluoroethylphosphine oxide,
Is preferred.

Specific examples of the compound in which any one of R ¹ , R ² and R ³ is a fluorine atom include, for example,
Dimethyl fluorophosphate,
Ethyl methyl fluorophosphate,
Methyl n-propyl fluorophosphate,
N-butylmethyl fluorophosphate,
Diethyl fluorophosphate,
Ethyl n-propyl fluorophosphate,
N-butylethyl fluorophosphate,
Di-n-propyl fluorophosphate,
N-butyl n-propyl fluorophosphate,
Di-n-butylmethyl fluorophosphate,
Cyclopentylmethyl fluorophosphate,
Cyclopentylethyl fluorophosphate,
Cyclopentyl n-propyl fluorophosphate,
Cyclopentyl n-butyl fluorophosphate,
Dicyclopentyl fluorophosphate,
Cyclohexylmethyl fluorophosphate,
Cyclohexyl ethyl fluorophosphate,
Cyclohexyl n-propyl fluorophosphate,
Cyclohexyl n-butyl fluorophosphate,
Dicyclohexyl fluorophosphate,
Bis (trifluoromethyl) fluorophosphate,
Methyl fluorophosphate (trifluoromethyl),
Ethyl fluorophosphate (trifluoromethyl),
N-propyl fluorophosphate (trifluoromethyl),
Bis (2,2,2-trifluoroethyl) fluorophosphate,
Methyl fluorophosphate (2,2,2-trifluoroethyl),
Ethyl fluorophosphate (2,2,2-trifluoroethyl),
N-propyl fluorophosphate (2,2,2-trifluoroethyl),
Fluorophosphoric acid (2,2,2-trifluoroethyl) (trifluoromethyl),
Bis (fluorofluorophosphate) (pentafluoroethyl),
Methyl fluorophosphate (pentafluoroethyl),
Ethyl fluorophosphate (pentafluoroethyl),
N-propyl fluorophosphate (pentafluoroethyl),
Fluorophosphoric acid (pentafluoroethyl) (trifluoromethyl),
And fluorophosphoric acid (pentafluoroethyl) (2,2,2-trifluoroethyl).

Among the monofluorophosphates exemplified above,
Dimethyl fluorophosphate,
Ethyl methyl fluorophosphate,
Methyl n-propyl fluorophosphate,
Diethyl fluorophosphate,
Ethyl n-propyl fluorophosphate,
Di-n-propyl fluorophosphate,
Bis (trifluoromethyl) fluorophosphate,
Methyl fluorophosphate (trifluoromethyl),
Ethyl fluorophosphate (trifluoromethyl),
N-propyl fluorophosphate (trifluoromethyl),
Bis (2,2,2-trifluoroethyl) fluorophosphate,
Methyl fluorophosphate (2,2,2-trifluoroethyl),
Ethyl fluorophosphate (2,2,2-trifluoroethyl),
N-propyl fluorophosphate (2,2,2-trifluoroethyl),
Bis (fluorofluorophosphate) (pentafluoroethyl),
Methyl fluorophosphate (pentafluoroethyl),
Ethyl fluorophosphate (pentafluoroethyl),
N-propyl fluorophosphate (pentafluoroethyl),
Is preferred.

Specific examples of the compound in which any ^{two of} R ¹ , R ² and R ³ are fluorine atoms include
Methyl difluorophosphate,
Ethyl difluorophosphate,
N-propyl difluorophosphate,
N-butyl difluorophosphate,
Cyclopentyl difluorophosphate,
Cyclohexyl difluorophosphate,
Difluorophosphoric acid (trifluoromethyl),
Difluorophosphoric acid (2,2,2-trifluoroethyl),
And difluorophosphoric acid (pentafluoroethyl).

<1-2-2. Nitrile compound>
The type of nitrile compound is not particularly limited as long as it is a compound having a nitrile group in the molecule. Moreover, the compound which has two or more nitrile groups in 1 molecule may be sufficient. Specific examples of nitrile compounds include, for example,
Acetonitrile,
Propionitrile,
Butyronitrile,
Isobutyronitrile,
Valeronitrile,
Isovaleronitrile,
2-methylbutyronitrile,
Trimethylacetonitrile,
Hexanenitrile,
Cyclopentanecarbonitrile,
Cyclohexanecarbonitrile,
Acrylonitrile,
Methacrylonitrile,
Crotononitrile,
3-methylcrotononitrile,
2-methyl-2-butenenitryl,
2-pentenenitrile,
2-methyl-2-pentenenitrile,
3-methyl-2-pentenenitrile,
2-hexenenitrile,
Fluoroacetonitrile,
Difluoroacetonitrile,
Trifluoroacetonitrile,
2-fluoropropionitrile,
3-fluoropropionitrile,
2,2-difluoropropionitrile,
2,3-difluoropropionitrile,
3,3-difluoropropionitrile,
2,2,3-trifluoropropionitrile,
3,3,3-trifluoropropionitrile,
Mononitrile compounds such as pentafluoropropionitrile;

Malononitrile,
Succinonitrile,
2-methylsuccinonitrile,
Tetramethylsuccinonitrile,
Glutaronitrile,
2-methylglutaronitrile,
Adiponitrile,
Fumaronitrile,
Dinitrile compounds such as 2-methyleneglutaronitrile;

Tetranitrile compounds such as tetracyanoethylene;
Etc.

Among these,
Acetonitrile,
Propionitrile,
Butyronitrile,
Valeronitrile,
Crotononitrile,
3-methylcrotononitrile,
Malononitrile,
Succinonitrile,
Glutaronitrile,
Adiponitrile,
Fumaronitrile is preferred.

<1-2-3. Isocyanate compound>
The type of the isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Moreover, the compound which has multiple isocyanate groups in 1 molecule may be sufficient. Specific examples of the isocyanate compound include, for example,
Methyl isocyanate,
Ethyl isocyanate,
n-propyl isocyanate,
Isopropyl isocyanate,
n-butyl isocyanate,
t-butyl isocyanate,
Cyclopentyl isocyanate,
Cyclohexyl isocyanate,
Phenyl isocyanate,
Monoisocyanate compounds such as vinyl isocyanate allyl isocyanate;

Diisocyanate compounds such as methane diisocyanate 1,2-ethane diisocyanate 1,3-propane diisocyanate 1,4-dicyanate butane;

Methyl isocyanate formate,
Ethyl isocyanate formate methyl isocyanate acetate,
Ethyl isocyanate acetate,
n-propyl isocyanate acetate methyl 3-isocyanate propionate,
Ethyl 3-isocyanate propionate,
n-propyl 3-isocyanate propionate methyl 2-isocyanate propionate,
Ethyl 2-isocyanate propionate,
ester group-containing isocyanate compounds such as n-propyl 2-isocyanate propionate;

Isocyanate trimethylsilane,
Isocyanate triethylsilane,
Isocyanate tri n-propyl silane isocyanate trimethoxy silane,
Isocyanate triethoxysilane,
Isocyanate tri-n-propoxysilane isocyanate methyltrimethylsilane,
Isocyanate methyltriethylsilane,
2-isocyanatoethyltrimethylsilane,
2-isocyanatoethyltriethylsilane,
3-isocyanatopropyltrimethylsilane,
3-isocyanatopropyltriethylsilane,
Isocyanate methyltrimethoxysilane,
Isocyanate methyltriethoxysilane,
2-isocyanatoethyltrimethoxysilane,
2-isocyanatoethyltriethoxysilane,
3-isocyanatopropyltrimethoxysilane,
Silicon-containing isocyanate compounds such as 3-isocyanatopropyltriethoxysilane;

Isocyanate dimethyl phosphate,
Isocyanatoethyl methyl phosphate,
Isocyanate methyl n-propyl phosphate,
Isocyanate n-butylmethyl phosphate,
Diethyl isocyanate phosphate,
Isocyanatoethyl n-propyl phosphate,
Isocyanate n-butylethyl phosphate,
Isocyanate di-n-propyl phosphate,
Isocyanate n-butyl n-propyl phosphate,
Phosphorus-containing isocyanate compounds such as isocyanate di-n-butylmethyl phosphate;
Etc.

Among these,
Methyl isocyanate,
Ethyl isocyanate,
n-propyl isocyanate,
n-butyl isocyanate,
Methane diisocyanate 1,2-ethane diisocyanate 1,3-propane diisocyanate 1,4-dicyanate butane methyl isocyanate formate,
Ethyl isocyanate formate methyl isocyanate acetate,
Ethyl isocyanate acetate,
Isocyanate trimethylsilane,
Isocyanate triethylsilane,
Isocyanate tri n-propyl silane isocyanate trimethoxy silane,
Isocyanate triethoxysilane,
Isocyanate tri-n-propoxysilane isocyanate dimethyl phosphate,
Isocyanatoethyl methyl phosphate,
Isocyanate diethyl phosphate is preferred.

［一般式（２）中、Ｘ^１１，Ｘ^１２は、各々独立に１価の置換基を表わす。］ <1-2-4. Phosphazene Compound>
In the present invention, the “phosphazene compound” refers to a compound having a structural unit represented by —PX ^a X ^b ═N— (where X ^a and X ^b each independently represents a monovalent substituent). Depending on the number of structural units described above and their bonding state, they are classified into monophosphazenes consisting of only one structural unit, cyclic phosphazenes in which the structural units are linked in a cyclic manner, polyphosphazenes in which the structural units are linked in a chain, etc. Is done. The type of the phosphazene compound is not particularly limited, and a compound corresponding to any of the above classifications can be used. Among them, the cyclic phosphazene represented by the following general formula (2) and / or the following general formula (3 It is preferable to use a chain phosphazene represented by

[In General Formula (2), X ¹¹ and X ¹² each independently represents a monovalent substituent. ]

［一般式（３）中、Ｘ^２１，Ｘ^２２，Ｘ^２３，Ｘ^２４，Ｘ^２５，Ｘ^２６，Ｘ^２７は、各々独立に１価の置換基を表わす。］
なお、以下の記載において、Ｘ^１１，Ｘ^１２，Ｘ^２１，Ｘ^２２，Ｘ^２３，Ｘ^２４，Ｘ^２５，Ｘ^２６，Ｘ^２７を特に区別せずに指す場合には、「Ｘ」で表わすものとする。

[In General Formula (3), X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ each independently represents a monovalent substituent. ]
In the following description, when X ¹¹ , X ¹² , X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , and X ²⁷ are indicated without distinction, they are represented by “X”. And

  The monovalent substituent is not particularly limited as long as it does not detract from the gist of the present invention, but is a group represented by a halogen atom, an alkyl group, an aryl group, an acyl group, a carboxy group, or R—O— (R is an alkyl group). A group or an aryl group) (hereinafter sometimes abbreviated as “RO group” as appropriate). Among these, a halogen atom or an RO group is preferable from the viewpoint of electrochemical stability.

  As the halogen atom, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom is particularly preferable. On the other hand, the RO group is preferably an alkyl group having 1 to 6 carbon atoms when R is an alkyl group. Specific examples of the alkyl group preferable as R include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and the like, and a methyl group or an ethyl group is particularly preferable. On the other hand, when R is an aryl group, a phenyl group, a tolyl group, a naphthyl group and the like are preferable, and a phenyl group is particularly preferable. In addition, the hydrogen which the alkyl group or aryl group of R has may be substituted with a halogen atom. In particular, substitution with fluorine is preferable because the electrochemical stability is increased. The above Xs may all be the same type of substituent, but two or more different types of substituents may be combined.

  In general formula (2), n represents an integer of usually 3 or more and 10 or less, preferably 5 or less. In the general formula (3), m represents an integer of usually 0 or more and usually 10 or less, preferably 3 or less. When n and m exceed 10, when these compounds are contained in the electrolytic solution, the viscosity increases, and the battery performance of the load characteristics may be deteriorated due to the decrease in conductivity.

  The molecular weights of the compounds of general formula (2) and general formula (3) are usually in the range of 200 or more and 2000 or less, preferably 1000 or less. If the molecular weight is too high, poor dissolution may occur or load characteristics may deteriorate due to increased viscosity.

<1-2-5. Disulfonic acid ester compound>
The type of the disulfonic acid ester compound is not particularly limited as long as it is a compound having two sulfonic acid ester structures in the molecule. Specific examples of the chain disulfonic acid ester include, for example,
Ethanediol dimethanesulfonate,
Ethanediol diethanesulfonate,
Ethanediol dipropanesulfonate,
Ethanediol dibutanesulfonate,
Ethanediol bis (trifluoromethanesulfonate),
Ethanediol bis (pentafluoroethanesulfonate),
Ethanediol bis (heptafluoropropane sulfonate),
Ethanediol bis (perfluorobutanesulfonate),
Ethanediol bis (perfluoropentanesulfonate),
Ethanediol bis (perfluorohexanesulfonate),
Ethanediol bis (perfluorooctane sulfonate),
Ethanediol bis (perfluoro-1-methylethanesulfonate),
Ethanediol bis (perfluoro-1,1-dimethylethanesulfonate),
Ethanediol bis (perfluoro-3-methylbutanesulfonate),
Ethanediol di (fluoromethanesulfonate),
Ethanediol bis (difluoromethanesulfonate),
Ethanediol di (2-fluoroethanesulfonate),
Ethanediol bis (1,1-difluoroethanesulfonate),
Ethanediol bis (1,2-difluoroethanesulfonate),
Ethanediol bis (2,2-difluoroethanesulfonate),
Ethanediol bis (1,1,2-trifluoroethanesulfonate),
Ethanediol bis (1,2,2-trifluoroethanesulfonate),
Ethanediol bis (2,2,2-trifluoroethanesulfonate),
Ethanediol bis (1,1,2,2-tetrafluoroethanesulfonate),
Ethanediol bis (1,2,2,2-tetrafluoroethanesulfonate),
Ethanediol di (1-fluoro-1-methylethanesulfonate),
Ethanediol bis (1,2,2,2-tetrafluoro-1-methylethanesulfonate),
Ethanediol bis (1,1-difluoro-2-methylpropanesulfonate),
Ethanediol bis (1,2,2,3,3,3-hexafluoro-1-methylpropanesulfonate),
Ethanediol di (2-fluoro-1-fluoromethylethanesulfonate),
Ethanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
Ethanediol bis (1-trifluoromethylethanesulfonate),
Ethanediol di (1-methyl-1-trifluoromethylethanesulfonate),
Ethanediol disulfonates such as ethanediol bis (1-trifluoromethylhexanesulfonate);

1,2-propanediol dimethanesulfonate,
1,2-propanediol diethanesulfonate,
1,2-propanediol dipropanesulfonate,
1,2-propanediol dibutanesulfonate,
1,2-propanediol bis (trifluoromethanesulfonate),
1,2-propanediol bis (pentafluoroethanesulfonate),
1,2-propanediol bis (heptafluoropropane sulfonate),
1,2-propanediol bis (perfluorobutane sulfonate),
1,2-propanediol bis (perfluoropentane sulfonate),
1,2-propanediol bis (perfluorohexanesulfonate),
1,2-propanediol bis (perfluorooctane sulfonate),
1,2-propanediol bis (perfluoro-1-methylethanesulfonate),
1,2-propanediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,2-propanediol bis (perfluoro-3-methylbutanesulfonate),
1,2-propanediol di (fluoromethanesulfonate),
1,2-propanediol bis (difluoromethanesulfonate),
1,2-propanediol di (2-fluoroethanesulfonate),
1,2-propanediol bis (1,1-difluoroethanesulfonate),
1,2-propanediol bis (1,2-difluoroethanesulfonate),
1,2-propanediol bis (2,2-difluoroethanesulfonate),
1,2-propanediol bis (1,1,2-trifluoroethanesulfonate),
1,2-propanediol bis (1,2,2-trifluoroethanesulfonate),
1,2-propanediol bis (2,2,2-trifluoroethanesulfonate),
1,2-propanediol bis (1,1,2,2-tetrafluoroethanesulfonate),
1,2-propanediol bis (1,2,2,2-tetrafluoroethanesulfonate),
1,2-propanediol di (1-fluoro-1-methylethanesulfonate),
1,2-propanediol bis (1,2,2,2-tetrafluoro-1-methylethanesulfonate),
1,2-propanediol bis (1,1-difluoro-2-methylpropanesulfonate),
1,2-propanediol bis (1,2,2,3,3,3-hexafluoro-1-methylpropanesulfonate),
1,2-propanediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,2-propanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,2-propanediol bis (1-trifluoromethylethanesulfonate),
1,2-propanediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,2-propanediol disulfonates such as 1,2-propanediol bis (1-trifluoromethylhexanesulfonate);

1,3-propanediol dimethanesulfonate,
1,3-propanediol diethanesulfonate,
1,3-propanediol dipropanesulfonate,
1,3-propanediol dibutanesulfonate,
1,3-propanediol bis (trifluoromethanesulfonate),
1,3-propanediol bis (pentafluoroethanesulfonate),
1,3-propanediol bis (heptafluoropropane sulfonate),
1,3-propanediol bis (perfluorobutane sulfonate),
1,3-propanediol bis (perfluoropentane sulfonate),
1,3-propanediol bis (perfluorohexanesulfonate),
1,3-propanediol bis (perfluorooctane sulfonate),
1,3-propanediol bis (perfluoro-1-methylethanesulfonate),
1,3-propanediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,3-propanediol bis (perfluoro-3-methylbutanesulfonate),
1,3-propanediol di (fluoromethanesulfonate),
1,3-propanediol bis (difluoromethanesulfonate),
1,3-propanediol di (2-fluoroethanesulfonate),
1,3-propanediol bis (1,1-difluoroethanesulfonate),
1,3-propanediol bis (1,2-difluoroethanesulfonate),
1,3-propanediol bis (2,2-difluoroethanesulfonate),
1,3-propanediol bis (1,1,2-trifluoroethanesulfonate),
1,3-propanediol bis (1,2,2-trifluoroethanesulfonate),
1,3-propanediol bis (2,2,2-trifluoroethanesulfonate),
1,3-propanediol bis (1,1,2,2-tetrafluoroethanesulfonate),
1,3-propanediol bis (1,2,2,2-tetrafluoroethanesulfonate),
1,3-propanediol di (1-fluoro-1-methylethanesulfonate),
1,3-propanediol bis (1,2,2,2-tetrafluoro-1-methylethanesulfonate),
1,3-propanediol bis (1,1-difluoro-2-methylpropanesulfonate),
1,3-propanediol bis (1,2,2,3,3,3-hexafluoro-1-methylpropanesulfonate),
1,3-propanediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,3-propanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,3-propanediol bis (1-trifluoromethylethanesulfonate),
1,3-propanediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,3-propanediol disulfonates such as 1,3-propanediol bis (1-trifluoromethylhexanesulfonate);

1,2-butanediol dimethanesulfonate,
1,2-butanediol diethane sulfonate,
1,2-butanediol bis (trifluoromethanesulfonate),
1,2-butanediol bis (pentafluoroethanesulfonate),
1,2-butanediol bis (heptafluoropropane sulfonate),
1,2-butanediol bis (perfluorobutane sulfonate),
1,2-butanediol bis (perfluoro-1-methylethanesulfonate),
1,2-butanediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,2-butanediol di (fluoromethanesulfonate),
1,2-butanediol bis (difluoromethanesulfonate),
1,2-butanediol di (2-fluoroethanesulfonate),
1,2-butanediol bis (2,2-difluoroethanesulfonate),
1,2-butanediol bis (2,2,2-trifluoroethanesulfonate),
1,2-butanediol di (1-fluoro-1-methylethanesulfonate),
1,2-butanediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,2-butanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,2-butanediol bis (1-trifluoromethylethanesulfonate),
1,2-butanediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,2-butanediol disulfonates such as 1,2-butanediol bis (1-trifluoromethylhexanesulfonate);

1,3-butanediol dimethanesulfonate,
1,3-butanediol diethane sulfonate,
1,3-butanediol bis (trifluoromethanesulfonate),
1,3-butanediol bis (pentafluoroethanesulfonate),
1,3-butanediol bis (heptafluoropropane sulfonate),
1,3-butanediol bis (perfluorobutane sulfonate),
1,3-butanediol bis (perfluoro-1-methylethanesulfonate),
1,3-butanediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,3-butanediol di (fluoromethanesulfonate),
1,3-butanediol bis (difluoromethanesulfonate),
1,3-butanediol di (2-fluoroethanesulfonate),
1,3-butanediol bis (2,2-difluoroethanesulfonate),
1,3-butanediol bis (2,2,2-trifluoroethanesulfonate),
1,3-butanediol di (1-fluoro-1-methylethanesulfonate),
1,3-butanediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,3-butanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,3-butanediol bis [(1-trifluoromethyl) ethanesulfonate],
1,3-butanediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,3-butanediol disulfonates such as 1,3-butanediol bis (1-trifluoromethylhexanesulfonate);

1,4-butanediol dimethanesulfonate,
1,4-butanediol diethane sulfonate,
1,4-butanediol dipropanesulfonate,
1,4-butanediol dibutanesulfonate,
1,4-butanediol bis (trifluoromethanesulfonate),
1,4-butanediol bis (pentafluoroethanesulfonate),
1,4-butanediol bis (heptafluoropropane sulfonate),
1,4-butanediol bis (perfluorobutane sulfonate),
1,4-butanediol bis (perfluoropentane sulfonate),
1,4-butanediol bis (perfluorohexanesulfonate),
1,4-butanediol bis (perfluorooctane sulfonate),
1,4-butanediol bis (perfluoro-1-methylethanesulfonate),
1,4-butanediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,4-butanediol bis (perfluoro-3-methylbutanesulfonate),
1,4-butanediol di (fluoromethanesulfonate),
1,4-butanediol bis (difluoromethanesulfonate),
1,4-butanediol di (2-fluoroethanesulfonate),
1,4-butanediol bis (1,1-difluoroethanesulfonate),
1,4-butanediol bis (1,2-difluoroethanesulfonate),
1,4-butanediol bis (2,2-difluoroethanesulfonate),
1,4-butanediol bis (1,1,2-trifluoroethanesulfonate),
1,4-butanediol bis (1,2,2-trifluoroethanesulfonate),
1,4-butanediol bis (2,2,2-trifluoroethanesulfonate),
1,4-butanediol bis (1,1,2,2-tetrafluoroethanesulfonate),
1,4-butanediol bis (1,2,2,2-tetrafluoroethanesulfonate),
1,4-butanediol di (1-fluoro-1-methylethanesulfonate),
1,4-butanediol bis (1,2,2,2-tetrafluoro-1-methylethanesulfonate),
1,4-butanediol bis (1,1-difluoro-2-methylpropanesulfonate),
1,4-butanediol bis (1,2,2,3,3,3-hexafluoro-1-methylpropanesulfonate),
1,4-butanediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,4-butanediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,4-butanediol bis (1-trifluoromethylethanesulfonate),
1,4-butanediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,4-butanediol disulfonates such as 1,4-butanediol bis (1-trifluoromethylhexanesulfonate);

1,4-benzenediol dimethanesulfonate,
1,4-benzenediol diethanesulfonate,
1,4-benzenediol bis (trifluoromethanesulfonate),
1,4-benzenediol bis (pentafluoroethanesulfonate),
1,4-benzenediol bis (heptafluoropropane sulfonate),
1,4-benzenediol bis (perfluorobutane sulfonate),
1,4-benzenediol bis (perfluoro-1-methylethanesulfonate),
1,4-benzenediol bis (perfluoro-1,1-dimethylethanesulfonate),
1,4-benzenediol di (fluoromethanesulfonate),
1,4-benzenediol di (2-fluoroethanesulfonate),
1,4-benzenediol bis (2,2-difluoroethanesulfonate),
1,4-benzenediol bis (2,2,2-trifluoroethanesulfonate),
1,4-benzenediol di (1-fluoro-1-methylethanesulfonate),
1,4-benzenediol di (2-fluoro-1-fluoromethylethanesulfonate),
1,4-benzenediol bis (2,2,2-trifluoro-1-trifluoromethylethanesulfonate),
1,4-benzenediol bis (1-trifluoromethylethanesulfonate),
1,4-benzenediol di (1-methyl-1-trifluoromethylethanesulfonate),
1,4-benzenediol disulfonates such as 1,4-benzenediol bis (1-trifluoromethylhexanesulfonate);
Etc.

Among these,
Ethanediol dimethanesulfonate,
Ethanediol diethanesulfonate,
Ethanediol bis (trifluoromethanesulfonate),
Ethanediol bis (pentafluoroethanesulfonate),
Ethanediol di (fluoromethanesulfonate),
Ethanediol bis (difluoromethanesulfonate),
Ethanediol di (2-fluoroethanesulfonate),
Ethanediol bis (2,2-difluoroethanesulfonate),
Ethanediol disulfonates such as ethanediol bis (2,2,2-trifluoroethanesulfonate);

1,2-propanediol dimethanesulfonate,
1,2-propanediol diethanesulfonate,
1,2-propanediol bis (trifluoromethanesulfonate),
1,2-propanediol bis (pentafluoroethanesulfonate),
1,2-propanediol di (fluoromethanesulfonate),
1,2-propanediol bis (difluoromethanesulfonate),
1,2-propanediol di (2-fluoroethanesulfonate),
1,2-propanediol bis (2,2-difluoroethanesulfonate),
1,2-propanediol disulfonates such as 1,2-propanediol bis (2,2,2-trifluoroethanesulfonate);

1,3-propanediol dimethanesulfonate,
1,3-propanediol diethanesulfonate,
1,3-propanediol bis (trifluoromethanesulfonate),
1,3-propanediol bis (pentafluoroethanesulfonate),
1,3-propanediol di (fluoromethanesulfonate),
1,3-propanediol bis (difluoromethanesulfonate),
1,3-propanediol di (2-fluoroethanesulfonate),
1,3-propanediol bis (2,2-difluoroethanesulfonate),
1,3-propanediol disulfonates such as 1,3-propanediol bis (2,2,2-trifluoroethanesulfonate);

1,2-butanediol dimethanesulfonate,
1,2-butanediol diethane sulfonate,
1,2-butanediol bis (trifluoromethanesulfonate)
1,2-butanediol bis (pentafluoroethanesulfonate),
1,2-butanediol di (fluoromethanesulfonate),
1,2-butanediol bis (difluoromethanesulfonate),
1,2-butanediol di (2-fluoroethanesulfonate),
1,2-butanediol bis (2,2-difluoroethanesulfonate),
1,2-butanediol disulfonates such as 1,2-butanediol bis (2,2,2-trifluoroethanesulfonate);

1,3-butanediol dimethanesulfonate,
1,3-butanediol diethane sulfonate,
1,3-butanediol bis (trifluoromethanesulfonate),
1,3-butanediol bis (pentafluoroethanesulfonate),
1,3-butanediol di (fluoromethanesulfonate),
1,3-butanediol bis (difluoromethanesulfonate),
1,3-butanediol di (2-fluoroethanesulfonate),
1,3-butanediol bis (2,2-difluoroethanesulfonate),
1,3-butanediol disulfonates such as 1,3-butanediol bis (2,2,2-trifluoroethanesulfonate);

1,4-butanediol dimethanesulfonate,
1,4-butanediol diethane sulfonate,
1,4-butanediol bis (trifluoromethanesulfonate),
1,4-butanediol bis (pentafluoroethanesulfonate),
1,4-butanediol di (fluoromethanesulfonate),
1,4-butanediol bis (difluoromethanesulfonate),
1,4-butanediol di (2-fluoroethanesulfonate),
1,4-butanediol bis (2,2-difluoroethanesulfonate),
1,4-butanediol disulfonates such as 1,4-butanediol bis (2,2,2-trifluoroethanesulfonate);
Etc. are preferred.

Furthermore, among these,
Ethanediol bis (trifluoromethanesulfonate),
Ethanediol bis (pentafluoroethanesulfonate),
Ethanediol di (fluoromethanesulfonate),
Ethanediol di (2-fluoroethanesulfonate),
Ethanediol disulfonates such as ethanediol bis (2,2,2-trifluoroethanesulfonate);

1,2-propanediol bis (trifluoromethanesulfonate),
1,2-propanediol bis (pentafluoroethanesulfonate),
1,2-propanediol di (fluoromethanesulfonate),
1,2-propanediol di (2-fluoroethanesulfonate),
1,2-propanediol disulfonates such as 1,2-propanediol bis (2,2,2-trifluoroethanesulfonate);

1,3-propanediol bis (trifluoromethanesulfonate),
1,3-propanediol bis (pentafluoroethanesulfonate),
1,3-propanediol di (2-fluoroethanesulfonate),
1,3-propanediol disulfonates such as 1,3-propanediol bis (2,2,2-trifluoroethanesulfonate);

1,2-butanediol bis (trifluoromethanesulfonate),
1,2-butanediol bis (pentafluoroethanesulfonate),
1,2-butanediol di (fluoromethanesulfonate),
1,2-butanediol di (2-fluoroethanesulfonate),
1,2-butanediol disulfonates such as 1,2-butanediol bis (2,2,2-trifluoroethanesulfonate);

1,3-butanediol bis (trifluoromethanesulfonate),
1,3-butanediol bis (pentafluoroethanesulfonate),
1,3-butanediol di (fluoromethanesulfonate),
1,3-butanediol di (2-fluoroethanesulfonate),
1,3-butanediol disulfonates such as 1,3-butanediol bis (2,2,2-trifluoroethanesulfonate);

1,4-butanediol bis (trifluoromethanesulfonate),
1,4-butanediol bis (pentafluoroethanesulfonate),
1,4-butanediol di (fluoromethanesulfonate),
1,4-butanediol di (2-fluoroethanesulfonate),
1,4-butanediol disulfonates such as 1,4-butanediol bis (2,2,2-trifluoroethanesulfonate);
Etc. are particularly preferred.

Specific examples of the cyclic disulfonic acid ester include, for example,
1,5,2,4-dioxadithian-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-fluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6,6-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6-fluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6,6-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,6-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,6-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3,6,6-tetramethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3,6,6-tetrafluoro-2,2,4,4-tetraoxide,

1,4,2,5-dioxadithian-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3-methyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,3-dimethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3-fluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,3-difluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,6-dimethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,6-difluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,3,6,6-tetramethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,3,6,6-tetrafluoro-2,2,5,5-tetraoxide,

1,5,2,4-dioxadithian-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-methyl-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-dimethyl-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-fluoro-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-difluoro-6-one-2,2,4,4-tetraoxide,

1,5,2,4-dioxadithiepan-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-3-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-3,3-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-3-fluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-3,3-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-6-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiepan-6,7-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithiocan-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithionan-2,2,4,4-tetraoxide and the like,

1,5,2,4-dioxadithian-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-fluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6-methyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6,6-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6-fluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-6,6-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,6-dimethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,6-difluoro-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3,6,6-tetramethyl-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3,6,6-tetrafluoro-2,2,4,4-tetraoxide,

1,4,2,5-dioxadithian-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3-methyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,3-dimethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3-fluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,3-difluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithian-3,6-dimethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,6-difluoro-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,3,6,6-tetramethyl-2,2,5,5-tetraoxide,
1,4,2,5-dioxadithiane-3,3,6,6-tetrafluoro-2,2,5,5-tetraoxide,

1,5,2,4-dioxadithian-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-methyl-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3,3-dimethyl-6-one-2,2,4,4-tetraoxide,
1,5,2,4-dioxadithian-3-fluoro-6-one-2,2,4,4-tetraoxide,
A compound having a 6-membered ring structure such as 1,5,2,4-dioxadithian-3,3-difluoro-6-one-2,2,4,4-tetraoxide is preferable.

<1-2-6. Sulfide compound>
The sulfide compound is not particularly limited as long as it is a compound having a sulfide structure in the molecule. Specific examples of the sulfide compound include, for example,
Dimethyl sulfide,
Diethyl sulfide,
Di-n-propyl sulfide,
Diisopropyl sulfide,
Di-n-butyl sulfide,
Diisobutyl sulfide,
Di-tert-butyl sulfide,
Dicyclopentyl sulfide,
Dicyclohexyl sulfide,

Ethyl methyl sulfide,
Methylpropyl sulfide,
Methyl isopropyl sulfide,
Methyl n-butyl sulfide,
Methyl isobutyl sulfide,
Methyl tert-butyl sulfide,
Methylcyclopentyl sulfide,
Methyl cyclohexyl sulfide,
Ethylpropyl sulfide,
Ethyl isopropyl sulfide,
Ethyl n-butyl sulfide,
Ethyl isobutyl sulfide,
Ethyl tert-butyl sulfide,
Ethylcyclopentyl sulfide,
Ethyl cyclohexyl sulfide,

Diphenyl sulfide,
Di (2-toluyl) sulfide,
Di (3-toluyl) sulfide,
Di (4-toluyl) sulfide,
Divinyl sulfide,
Diallyl sulfide,
Dibenzyl sulfide,

Methyl phenyl sulfide,
Methyl (2-toluyl) sulfide,
Methyl (3-toluyl) sulfide,
Methyl (4-toluyl) sulfide,
Methyl vinyl sulfide,
Methyl allyl sulfide,
Methylbenzyl sulfide,
Ethyl phenyl sulfide,
Ethyl (2-toluyl) sulfide,
Ethyl (3-toluyl) sulfide,
Ethyl (4-toluyl) sulfide,
Ethyl vinyl sulfide,
Ethyl allyl sulfide,
Ethyl benzyl sulfide,

Phenylpropyl sulfide,
Phenyl isopropyl sulfide,
Phenyl n-butyl sulfide,
Phenyl isobutyl sulfide,
Phenyl tert-butyl sulfide,
Phenylcyclopentyl sulfide,
Phenylcyclohexyl sulfide,
Phenyl (2-toluyl) sulfide,
Phenyl (3-toluyl) sulfide,
Phenyl (4-toluyl) sulfide,
Phenyl vinyl sulfide,
Phenylallyl sulfide,
Phenylbenzyl sulfide,

Bis (fluoromethyl) sulfide,
Bis (difluoromethyl) sulfide,
Bis (trifluoromethyl) sulfide,
Di (1-fluoroethyl) sulfide,
Di (2-fluoroethyl) sulfide,
Bis (2,2,2-trifluoroethyl) sulfide,
Bis (perfluoroethyl) sulfide,
Bis (3,3,3-trifluoro-n-propyl) sulfide,
Bis (2,2,3,3,3-pentafluoro-n-propyl) sulfide,
Bis (perfluoro-n-propyl) sulfide,
Di (2-fluoroisopropyl) sulfide,
Bis (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) sulfide,
Bis (perfluoro-n-butyl) sulfide,
Di (2-fluoro-tert-butyl) sulfide,
Bis (perfluoro-tert-butyl) sulfide,
Di (2-fluorocyclohexyl) sulfide,
Di (3-fluorocyclohexyl) sulfide,
Di (4-fluorocyclohexyl) sulfide,
Bis (perfluorocyclohexyl) sulfide methyl (fluoromethyl) sulfide,

Methyl (difluoromethyl) sulfide,
Methyl (trifluoromethyl) sulfide,
Methyl (1-fluoroethyl) sulfide,
Methyl (2-fluoroethyl) sulfide,
Methyl (2,2,2-trifluoroethyl) sulfide,
Methyl (perfluoroethyl) sulfide,
Methyl (3,3,3-trifluoro-n-propyl) sulfide,
Methyl (2,2,3,3,3-pentafluoro-n-propyl) sulfide,
Methyl (perfluoro-n-propyl) sulfide,
Methyl (2-fluoroisopropyl) sulfide,
Methyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) sulfide,
Methyl (perfluoro-n-butyl) sulfide,
Methyl (2-fluoro-tert-butyl) sulfide,
Methyl (perfluoro-tert-butyl) sulfide,
Methyl (2-fluorocyclohexyl) sulfide,
Methyl (3-fluorocyclohexyl) sulfide,
Methyl (4-fluorocyclohexyl) sulfide,
Methyl (perfluorocyclohexyl) sulfide,

Ethyl (fluoromethyl) sulfide,
Ethyl (difluoromethyl) sulfide,
Ethyl (trifluoromethyl) sulfide,
Ethyl (1-fluoroethyl) sulfide,
Ethyl (2-fluoroethyl) sulfide,
Ethyl (2,2,2-trifluoroethyl) sulfide,
Ethyl (perfluoroethyl) sulfide,
Ethyl (3,3,3-trifluoro-n-propyl) sulfide,
Ethyl (2,2,3,3,3-pentafluoro-n-propyl) sulfide,
Ethyl (perfluoro-n-propyl) sulfide,
Ethyl (2-fluoroisopropyl) sulfide,
Ethyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) sulfide,
Ethyl (perfluoro-n-butyl) sulfide,
Ethyl (2-fluoro-tert-butyl) sulfide,
Ethyl (perfluoro-tert-butyl) sulfide,
Ethyl (2-fluorocyclohexyl) sulfide,
Ethyl (3-fluorocyclohexyl) sulfide,
Ethyl (4-fluorocyclohexyl) sulfide,
Ethyl (perfluorocyclohexyl) sulfide,

(2,2,2-trifluoroethyl) (fluoromethyl) sulfide,
(2,2,2-trifluoroethyl) (difluoromethyl) sulfide,
(2,2,2-trifluoroethyl) (trifluoromethyl) sulfide,
(2,2,2-trifluoroethyl) (1-fluoroethyl) sulfide,
(2,2,2-trifluoroethyl) (2-fluoroethyl) sulfide,
(2,2,2-trifluoroethyl) (perfluoroethyl) sulfide,
(2,2,2-trifluoroethyl) (3,3,3-trifluoro-n-propyl) sulfide,
(2,2,2-trifluoroethyl) (2,2,3,3,3-pentafluoro-n-propyl) sulfide,
(2,2,2-trifluoroethyl) (perfluoro-n-propyl) sulfide,
(2,2,2-trifluoroethyl) (2-fluoroisopropyl) sulfide,
(2,2,2-trifluoroethyl) (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) sulfide,
(2,2,2-trifluoroethyl) (perfluoro-n-butyl) sulfide,
(2,2,2-trifluoroethyl) (2-fluoro-tert-butyl) sulfide,
(2,2,2-trifluoroethyl) (perfluoro-tert-butyl) sulfide,
(2,2,2-trifluoroethyl) (2-fluorocyclohexyl) sulfide,
(2,2,2-trifluoroethyl) (3-fluorocyclohexyl) sulfide,
(2,2,2-trifluoroethyl) (4-fluorocyclohexyl) sulfide,
(2,2,2-trifluoroethyl) (perfluorocyclohexyl) sulfide,

Di (2-fluorophenyl) sulfide,
Di (3-fluorophenyl) sulfide,
Di (4-fluorophenyl) sulfide,
Bis (2,3-difluorophenyl) sulfide,
Bis (2,4-difluorophenyl) sulfide,
Bis (3,5-difluorophenyl) sulfide,
Bis (2,4,6-trifluorophenyl) sulfide,
Bis (perfluorophenyl) sulfide,
Di (1-fluorovinyl) sulfide,
Di (2-fluorovinyl) sulfide,
Bis (perfluorovinyl) sulfide,
Bis [(2-fluorophenyl) methyl] sulfide,
Bis [(3-fluorophenyl) methyl] sulfide,
Bis [(4-fluorophenyl) methyl] sulfide,
Bis [(perfluorophenyl) methyl] sulfide,

Methyl (2-fluorophenyl) sulfide,
Methyl (3-fluorophenyl) sulfide,
Methyl (4-fluorophenyl) sulfide,
Methyl (2,3-difluorophenyl) sulfide,
Methyl (2,4-difluorophenyl) sulfide,
Methyl (3,5-difluorophenyl) sulfide,
Methyl (2,4,6-trifluorophenyl) sulfide,
Methyl (perfluorophenyl) sulfide,
Methyl (1-fluorovinyl) sulfide,
Methyl (2-fluorovinyl) sulfide,
Methyl (perfluorovinyl) sulfide,
Methyl [(2-fluorophenyl) methyl] sulfide,
Methyl [(3-fluorophenyl) methyl] sulfide,
Methyl [(4-fluorophenyl) methyl] sulfide,
Methyl [(perfluorophenyl) methyl] sulfide,

Ethyl (2-fluorophenyl) sulfide,
Ethyl (3-fluorophenyl) sulfide,
Ethyl (4-fluorophenyl) sulfide,
Ethyl (2,3-difluorophenyl) sulfide,
Ethyl (2,4-difluorophenyl) sulfide,
Ethyl (3,5-difluorophenyl) sulfide,
Ethyl (2,4,6-trifluorophenyl) sulfide,
Ethyl (perfluorophenyl) sulfide,
Ethyl (1-fluorovinyl) sulfide,
Ethyl (2-fluorovinyl) sulfide,
Ethyl (perfluorovinyl) sulfide,
Ethyl [(2-fluorophenyl) ethyl] sulfide,
Ethyl [(3-fluorophenyl) methyl] sulfide,
Ethyl [(4-fluorophenyl) methyl] sulfide,
Ethyl [(perfluorophenyl) methyl] sulfide,

Phenyl (fluoromethyl) sulfide,
Phenyl (difluoromethyl) sulfide,
Phenyl (trifluoromethyl) sulfide,
Phenyl (1-fluoroethyl) sulfide,
Phenyl (2-fluoroethyl) sulfide,
Phenyl (2,2,2-trifluoroethyl) sulfide,
Phenyl (perfluoroethyl) sulfide,
Phenyl (3,3,3-trifluoro-n-propyl) sulfide,
Phenyl (2,2,3,3,3-pentafluoro-n-propyl) sulfide,
Phenyl (perfluoro-n-propyl) sulfide,
Phenyl (2-fluoroisopropyl) sulfide,
Phenyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) sulfide,
Phenyl (perfluoro-n-butyl) sulfide,
Phenyl (2-fluoro-tert-butyl) sulfide,
Phenyl (perfluoro-tert-butyl) sulfide,
Phenyl (2-fluorocyclohexyl) sulfide,
Phenyl (3-fluorocyclohexyl) sulfide,
Phenyl (4-fluorocyclohexyl) sulfide,
Phenyl (perfluorocyclohexyl) sulfide,
Phenyl (2-fluorophenyl) sulfide,
Phenyl (3-fluorophenyl) sulfide,
Phenyl (4-fluorophenyl) sulfide,
Phenyl (2,3-difluorophenyl) sulfide,
Phenyl (2,4-difluorophenyl) sulfide,
Phenyl (3,5-difluorophenyl) sulfide,
Phenyl (2,4,6-trifluorophenyl) sulfide,
Phenyl (perfluorophenyl) sulfide,
Phenyl (1-fluorovinyl) sulfide,
Phenyl (2-fluorovinyl) sulfide,
Phenyl (perfluorovinyl) sulfide,
Phenyl [(2-fluorophenyl) methyl] sulfide,
Phenyl [(3-fluorophenyl) methyl] sulfide,
Phenyl [(4-fluorophenyl) methyl] sulfide,
Phenyl [(perfluorophenyl) methyl] sulfide,

(2,2,2-trifluoroethyl) (2-fluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (3-fluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (4-fluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (2,3-difluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (2,4-difluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (3,5-difluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (2,4,6-trifluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (perfluorophenyl) sulfide,
(2,2,2-trifluoroethyl) (1-fluorovinyl) sulfide,
(2,2,2-trifluoroethyl) (2-fluorovinyl) sulfide,
(2,2,2-trifluoroethyl) (perfluorovinyl) sulfide,
(2,2,2-trifluoroethyl) [(2-fluorophenyl) methyl] sulfide,
(2,2,2-trifluoroethyl) [(3-fluorophenyl) methyl] sulfide,
(2,2,2-trifluoroethyl) [(4-fluorophenyl) methyl] sulfide,
(2,2,2-trifluoroethyl) [(perfluorophenyl) methyl] sulfide and the like.

<1-2-7. Disulfide Compound>
The type of the disulfide compound is not particularly limited as long as it is a compound having a disulfide structure in the molecule. Specific examples of the disulfide compound include, for example,
Dimethyl disulfide,
Diethyl disulfide,
Di-n-propyl disulfide,
Diisopropyl disulfide,
Di-n-butyl disulfide,
Diisobutyl disulfide,
Di-tert-butyl disulfide,
Dicyclopentyl disulfide,
Dicyclohexyl disulfide,

Ethyl methyl disulfide,
Methylpropyl disulfide,
Methyl isopropyl disulfide,
Methyl n-butyl disulfide,
Methyl isobutyl disulfide,
Methyl tert-butyl disulfide,
Methylcyclopentyl disulfide,
Methyl cyclohexyl disulfide ethyl propyl disulfide,
Ethyl isopropyl disulfide,
Ethyl n-butyl disulfide,
Ethyl isobutyl disulfide,
Ethyl tert-butyl disulfide,
Ethylcyclopentyl disulfide,
Ethylcyclohexyl disulfide,

Diphenyl disulfide,
Di (2-toluyl) disulfide,
Di (3-toluyl) disulfide,
Di (4-toluyl) disulfide,
Divinyl disulfide,
Diallyl disulfide,
Dibenzyl disulfide,

Methylphenyl disulfide,
Methyl (2-toluyl) disulfide,
Methyl (3-toluyl) disulfide,
Methyl (4-toluyl) disulfide,
Methyl vinyl disulfide,
Methyl allyl disulfide,
Methylbenzyl disulfide,
Ethylphenyl disulfide,
Ethyl (2-toluyl) disulfide,
Ethyl (3-toluyl) disulfide,
Ethyl (4-toluyl) disulfide,
Ethyl vinyl disulfide,
Ethyl allyl disulfide,
Ethylbenzyl disulfide,

Phenylpropyl disulfide,
Phenylisopropyl disulfide,
Phenyl n-butyl disulfide,
Phenyl isobutyl disulfide,
Phenyl tert-butyl disulfide,
Phenylcyclopentyl disulfide,
Phenylcyclohexyl disulfide,
Phenyl (2-toluyl) disulfide,
Phenyl (3-toluyl) disulfide,
Phenyl (4-toluyl) disulfide,
Phenyl vinyl disulfide,
Phenylallyl disulfide,
Phenylbenzyl disulfide,

Bis (fluoromethyl) disulfide,
Bis (difluoromethyl) disulfide,
Bis (trifluoromethyl) disulfide,
Di (1-fluoroethyl) disulfide,
Di (2-fluoroethyl) disulfide,
Bis (2,2,2-trifluoroethyl) disulfide,
Bis (perfluoroethyl) disulfide,
Bis (3,3,3-trifluoro-n-propyl) disulfide,
Bis (2,2,3,3,3-pentafluoro-n-propyl) disulfide,
Bis (perfluoro-n-propyl) disulfide,
Di (2-fluoroisopropyl) disulfide,
Bis (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) disulfide,
Bis (perfluoro-n-butyl) disulfide,
Di (2-fluoro-tert-butyl) disulfide,
Bis (perfluoro-tert-butyl) disulfide,
Di (2-fluorocyclohexyl) disulfide,
Di (3-fluorocyclohexyl) disulfide,
Di (4-fluorocyclohexyl) disulfide,
Bis (perfluorocyclohexyl) disulfide,

Methyl (fluoromethyl) disulfide,
Methyl (difluoromethyl) disulfide,
Methyl (trifluoromethyl) disulfide,
Methyl (1-fluoroethyl) disulfide,
Methyl (2-fluoroethyl) disulfide,
Methyl (2,2,2-trifluoroethyl) disulfide,
Methyl (perfluoroethyl) disulfide,
Methyl (3,3,3-trifluoro-n-propyl) disulfide,
Methyl (2,2,3,3,3-pentafluoro-n-propyl) disulfide,
Methyl (perfluoro-n-propyl) disulfide,
Methyl (2-fluoroisopropyl) disulfide,
Methyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) disulfide,
Methyl (perfluoro-n-butyl) disulfide,
Methyl (2-fluoro-tert-butyl) disulfide,
Methyl (perfluoro-tert-butyl) disulfide,
Methyl (2-fluorocyclohexyl) disulfide,
Methyl (3-fluorocyclohexyl) disulfide,
Methyl (4-fluorocyclohexyl) disulfide,
Methyl (perfluorocyclohexyl) disulfide,

Ethyl (fluoromethyl) disulfide,
Ethyl (difluoromethyl) disulfide,
Ethyl (trifluoromethyl) disulfide,
Ethyl (1-fluoroethyl) disulfide,
Ethyl (2-fluoroethyl) disulfide,
Ethyl (2,2,2-trifluoroethyl) disulfide,
Ethyl (perfluoroethyl) disulfide,
Ethyl (3,3,3-trifluoro-n-propyl) disulfide,
Ethyl (2,2,3,3,3-pentafluoro-n-propyl) disulfide,
Ethyl (perfluoro-n-propyl) disulfide,
Ethyl (2-fluoroisopropyl) disulfide,
Ethyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) disulfide,
Ethyl (perfluoro-n-butyl) disulfide,
Ethyl (2-fluoro-tert-butyl) disulfide,
Ethyl (perfluoro-tert-butyl) disulfide,
Ethyl (2-fluorocyclohexyl) disulfide,
Ethyl (3-fluorocyclohexyl) disulfide,
Ethyl (4-fluorocyclohexyl) disulfide,
Ethyl (perfluorocyclohexyl) disulfide,

(2,2,2-trifluoroethyl) (fluoromethyl) disulfide,
(2,2,2-trifluoroethyl) (difluoromethyl) disulfide,
(2,2,2-trifluoroethyl) (trifluoromethyl) disulfide,
(2,2,2-trifluoroethyl) (1-fluoroethyl) disulfide,
(2,2,2-trifluoroethyl) (2-fluoroethyl) disulfide,
(2,2,2-trifluoroethyl) (perfluoroethyl) disulfide,
(2,2,2-trifluoroethyl) (3,3,3-trifluoro-n-propyl) disulfide,
(2,2,2-trifluoroethyl) (2,2,3,3,3-pentafluoro-n-propyl) disulfide,
(2,2,2-trifluoroethyl) (perfluoro-n-propyl) disulfide,
(2,2,2-trifluoroethyl) (2-fluoroisopropyl) disulfide,
(2,2,2-trifluoroethyl) (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) disulfide,
(2,2,2-trifluoroethyl) (perfluoro-n-butyl) disulfide,
(2,2,2-trifluoroethyl) (2-fluoro-tert-butyl) disulfide,
(2,2,2-trifluoroethyl) (perfluoro-tert-butyl) disulfide,
(2,2,2-trifluoroethyl) (2-fluorocyclohexyl) disulfide,
(2,2,2-trifluoroethyl) (3-fluorocyclohexyl) disulfide,
(2,2,2-trifluoroethyl) (4-fluorocyclohexyl) disulfide,
(2,2,2-trifluoroethyl) (perfluorocyclohexyl) disulfide,

Di (2-fluorophenyl) disulfide,
Di (3-fluorophenyl) disulfide,
Di (4-fluorophenyl) disulfide,
Bis (2,3-difluorophenyl) disulfide,
Bis (2,4-difluorophenyl) disulfide,
Bis (3,5-difluorophenyl) disulfide,
Bis (2,4,6-trifluorophenyl) disulfide,
Bis (perfluorophenyl) disulfide,
Di (1-fluorovinyl) disulfide,
Di (2-fluorovinyl) disulfide,
Bis (perfluorovinyl) disulfide,
Bis [(2-fluorophenyl) methyl] disulfide,
Bis [(3-fluorophenyl) methyl] disulfide,
Bis [(4-fluorophenyl) methyl] disulfide,
Bis [(perfluorophenyl) methyl] disulfide,

Methyl (2-fluorophenyl) disulfide,
Methyl (3-fluorophenyl) disulfide,
Methyl (4-fluorophenyl) disulfide,
Methyl (2,3-difluorophenyl) disulfide,
Methyl (2,4-difluorophenyl) disulfide,
Methyl (3,5-difluorophenyl) disulfide,
Methyl (2,4,6-trifluorophenyl) disulfide,
Methyl (perfluorophenyl) disulfide,
Methyl (1-fluorovinyl) disulfide,
Methyl (2-fluorovinyl) disulfide,
Methyl (perfluorovinyl) disulfide,
Methyl [(2-fluorophenyl) methyl] disulfide,
Methyl [(3-fluorophenyl) methyl] disulfide,
Methyl [(4-fluorophenyl) methyl] disulfide,
Methyl [(perfluorophenyl) methyl] disulfide,

Ethyl (2-fluorophenyl) disulfide,
Ethyl (3-fluorophenyl) disulfide,
Ethyl (4-fluorophenyl) disulfide,
Ethyl (2,3-difluorophenyl) disulfide,
Ethyl (2,4-difluorophenyl) disulfide,
Ethyl (3,5-difluorophenyl) disulfide,
Ethyl (2,4,6-trifluorophenyl) disulfide,
Ethyl (perfluorophenyl) disulfide,
Ethyl (1-fluorovinyl) disulfide,
Ethyl (2-fluorovinyl) disulfide,
Ethyl (perfluorovinyl) disulfide,
Ethyl [(2-fluorophenyl) ethyl] disulfide,
Ethyl [(3-fluorophenyl) methyl] disulfide,
Ethyl [(4-fluorophenyl) methyl] disulfide,
Ethyl [(perfluorophenyl) methyl] disulfide,

Phenyl (fluoromethyl) disulfide,
Phenyl (difluoromethyl) disulfide,
Phenyl (trifluoromethyl) disulfide,
Phenyl (1-fluoroethyl) disulfide,
Phenyl (2-fluoroethyl) disulfide,
Phenyl (2,2,2-trifluoroethyl) disulfide,
Phenyl (perfluoroethyl) disulfide,
Phenyl (3,3,3-trifluoro-n-propyl) disulfide,
Phenyl (2,2,3,3,3-pentafluoro-n-propyl) disulfide,
Phenyl (perfluoro-n-propyl) disulfide,
Phenyl (2-fluoroisopropyl) disulfide,
Phenyl (2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl) disulfide,
Phenyl (perfluoro-n-butyl) disulfide,
Phenyl (2-fluoro-tert-butyl) disulfide,
Phenyl (perfluoro-tert-butyl) disulfide,
Phenyl (2-fluorocyclohexyl) disulfide,
Phenyl (3-fluorocyclohexyl) disulfide,
Phenyl (4-fluorocyclohexyl) disulfide,
Phenyl (perfluorocyclohexyl) disulfide,
Phenyl (2-fluorophenyl) disulfide,
Phenyl (3-fluorophenyl) disulfide,
Phenyl (4-fluorophenyl) disulfide,
Phenyl (2,3-difluorophenyl) disulfide,
Phenyl (2,4-difluorophenyl) disulfide,
Phenyl (3,5-difluorophenyl) disulfide,
Phenyl (2,4,6-trifluorophenyl) disulfide,
Phenyl (perfluorophenyl) disulfide,
Phenyl (1-fluorovinyl) disulfide,
Phenyl (2-fluorovinyl) disulfide,
Phenyl (perfluorovinyl) disulfide,
Phenyl [(2-fluorophenyl) methyl] disulfide,
Phenyl [(3-fluorophenyl) methyl] disulfide,
Phenyl [(4-fluorophenyl) methyl] disulfide,
Phenyl [(perfluorophenyl) methyl] disulfide,

(2,2,2-trifluoroethyl) (2-fluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (3-fluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (4-fluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (2,3-difluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (2,4-difluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (3,5-difluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (2,4,6-trifluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (perfluorophenyl) disulfide,
(2,2,2-trifluoroethyl) (1-fluorovinyl) disulfide,
(2,2,2-trifluoroethyl) (2-fluorovinyl) disulfide,
(2,2,2-trifluoroethyl) (perfluorovinyl) disulfide,
(2,2,2-trifluoroethyl) [(2-fluorophenyl) methyl] disulfide,
(2,2,2-trifluoroethyl) [(3-fluorophenyl) methyl] disulfide,
(2,2,2-trifluoroethyl) [(4-fluorophenyl) methyl] disulfide,
(2,2,2-trifluoroethyl) [(perfluorophenyl) methyl] disulfide and the like.

<1-2-8. Acid anhydride>
The type of the acid anhydride is not limited. Further, it may be a compound having a plurality of acid anhydride structures in one molecule. Examples of the acid anhydride used in the present invention include an anhydride of carboxylic acid, an anhydride of sulfonic acid, and an anhydride of carboxylic acid and sulfonic acid.

Specific examples of carboxylic anhydrides include
Acetic anhydride,
Propionic anhydride,
Butyric anhydride, crotonic anhydride,
Trifluoroacetic anhydride pentafluoropropionic anhydride succinic anhydride,
Glutaric anhydride,
maleic anhydride,
Citraconic anhydride,
Glutaconic anhydride,
Itaconic anhydride,
Diglycolic anhydride,
Cyclohexanedicarboxylic anhydride,
Cyclopentanetetracarboxylic dianhydride,
4-cyclohexene-1,2-dicarboxylic anhydride,
3,4,5,6-tetrahydrophthalic anhydride,
5-norbornene-2,3-dicarboxylic anhydride,
Phenylsuccinic anhydride,
2-phenylglutaric anhydride,
Phthalic anhydride,
Pyromellitic anhydride,
Fluorosuccinic anhydride,
Examples thereof include tetrafluorosuccinic anhydride.

Among these,
Succinic anhydride,
Glutaric anhydride,
maleic anhydride,
Citraconic anhydride,
Itaconic anhydride,
Diglycolic anhydride,
Cyclohexanedicarboxylic anhydride fluorosuccinic anhydride,
Tetrafluorosuccinic anhydride is preferred.

Specific examples of sulfonic anhydrides include
Methanesulfonic anhydride,
Ethanesulfonic anhydride,
Propanesulfonic anhydride,
Butanesulfonic anhydride,
Pentanesulfonic anhydride,
Hexanesulfonic anhydride,
Vinyl sulfonic anhydride,
Benzenesulfonic anhydride,
Trifluoromethanesulfonic anhydride,
2,2,2-trifluoroethanesulfonic anhydride,
Pentafluoroethanesulfonic anhydride,
1,2-ethanedisulfonic anhydride,
1,3-propanedisulfonic anhydride,
1,4-butanedisulfonic anhydride,
1,2-benzenedisulfonic anhydride,
Tetrafluoro-1,2-ethanedisulfonic anhydride,
Hexafluoro-1,3-propanedisulfonic anhydride,
Octafluoro-1,4-butanedisulfonic anhydride,
3-fluoro-1,2-benzenedisulfonic anhydride,
4-Fluoro-1,2-benzenedisulfonic anhydride 3,4,5,6-tetrafluoro-1,2-benzenedisulfonic anhydride and the like can be mentioned.

Among these,
Methanesulfonic anhydride,
Ethanesulfonic anhydride,
Propanesulfonic anhydride,
Butanesulfonic anhydride,
Vinyl sulfonic anhydride,
Benzenesulfonic anhydride,
Trifluoromethanesulfonic anhydride,
2,2,2-trifluoroethanesulfonic anhydride,
Pentafluoroethanesulfonic anhydride,
1,2-ethanedisulfonic anhydride,
1,3-propanedisulfonic anhydride,
1,2-benzenedisulfonic anhydride is preferred.

Specific examples of carboxylic acid and sulfonic acid anhydrides include:
Acetic acid methanesulfonic anhydride,
Ethane acetate anhydride,
Acetic acid propanesulfonic acid anhydride,
Propionic acid methanesulfonic anhydride,
Ethanesulfonic acid propionate,
Propionic acid propanesulfonic acid anhydride,
Trifluoroacetic acid methanesulfonic anhydride,
Trifluoroacetic acid ethanesulfonic anhydride,
Trifluoroacetic acid propanesulfonic acid anhydride,
Acetic acid trifluoromethanesulfonic anhydride,
Acetic acid 2,2,2-trifluoroethanesulfonic anhydride,
Acetic acid pentafluoroethanesulfonic anhydride,
Trifluoroacetic acid trifluoromethanesulfonic anhydride,
Trifluoroacetic acid 2,2,2-trifluoroethanesulfonic anhydride,
Trifluoroacetic acid pentafluoroethanesulfonic anhydride,
3-sulfopropionic anhydride,
2-methyl-3-sulfopropionic anhydride,
2,2-dimethyl-3-sulfopropionic anhydride,
2-ethyl-3-sulfopropionic anhydride,
2,2-diethyl-3-sulfopropionic anhydride,
2-fluoro-3-sulfopropionic anhydride,
2,2-difluoro-3-sulfopropionic anhydride,
2,2,3,3-tetrafluoro-3-sulfopropionic anhydride,
2-sulfobenzoic anhydride,
3-fluoro-2-sulfobenzoic anhydride,
4-fluoro-2-sulfobenzoic anhydride,
5-fluoro-2-sulfobenzoic anhydride,
6-fluoro-2-sulfobenzoic anhydride,
3,6-difluoro-2-sulfobenzoic anhydride,
3,4,5,6-tetrafluoro-2-sulfobenzoic anhydride,
3-trifluoromethyl-2-sulfobenzoic anhydride,
4-trifluoromethyl-2-sulfobenzoic anhydride,
5-trifluoromethyl-2-sulfobenzoic anhydride,
Examples include 6-trifluoromethyl-2-sulfobenzoic anhydride.

Among these,
Acetic acid methanesulfonic anhydride,
Ethane acetate anhydride,
Acetic acid propanesulfonic acid anhydride,
Propionic acid methanesulfonic anhydride,
Ethanesulfonic acid propionate,
Propionic acid propanesulfonic acid anhydride,
Trifluoroacetic acid methanesulfonic anhydride,
Trifluoroacetic acid ethanesulfonic anhydride,
Trifluoroacetic acid propanesulfonic acid anhydride,
Acetic acid trifluoromethanesulfonic anhydride,
Acetic acid 2,2,2-trifluoroethanesulfonic anhydride,
Acetic acid pentafluoroethanesulfonic anhydride,
Trifluoroacetic acid trifluoromethanesulfonic anhydride,
Trifluoroacetic acid 2,2,2-trifluoroethanesulfonic anhydride,
Trifluoroacetic acid pentafluoroethanesulfonic anhydride,
2-sulfobenzoic anhydride,
3-fluoro-2-sulfobenzoic anhydride,
4-fluoro-2-sulfobenzoic anhydride,
5-fluoro-2-sulfobenzoic anhydride,
6-Fluoro-2-sulfobenzoic anhydride is preferred.

<1-2-9. Lactone compound having a substituent at the α-position>
The lactone compound having a substituent at the α-position is not particularly limited,
α-methyl-β-propiolactone,
α-ethyl-β-propiolactone,
α-propyl-β-propiolactone,
α-vinyl-β-propiolactone,
α-allyl-β-propiolactone,
α-phenyl-β-propiolactone,
α-tolyl-β-propiolactone,
α-naphthyl-β-propiolactone,
α-fluoro-β-propiolactone,
α, α-dimethyl-β-propiolactone,
α, α-diethyl-β-propiolactone,
α-ethyl-α-methyl-β-propiolactone,
α-methyl-α-phenyl-β-propiolactone,
α, α-diphenyl-β-propiolactone,
α, α-ditolyl-β-propiolactone,
α, α-bis (dimethylphenyl) -β-propiolactone,
α, α-dinaphthyl-β-propiolactone,
α, α-divinyl-β-propiolactone,
α, α-diallyl-β-propiolactone,
α, α-dibenzyl-β-propiolactone,
α, α-diphenethyl-β-propiolactone,
β-propiolactone derivatives such as α, α-difluoro-β-propiolactone;

α-methyl-β-butyrolactone,
α-ethyl-β-butyrolactone,
α-propyl-β-butyrolactone,
α-vinyl-β-butyrolactone,
α-allyl-β-butyrolactone,
α-phenyl-β-butyrolactone,
α-tolyl-β-butyrolactone,
α-naphthyl-β-butyrolactone,
α-fluoro-β-butyrolactone,
α, α-dimethyl-β-butyrolactone,
α, α-diethyl-β-butyrolactone,
α-ethyl-α-methyl-β-butyrolactone,
α-methyl-α-phenyl-β-butyrolactone,
α, α-diphenyl-β-butyrolactone,
α, α-ditolyl-β-butyrolactone,
α, α-bis (dimethylphenyl) -β-butyrolactone,
α, α-dinaphthyl-β-butyrolactone,
α, α-divinyl-β-butyrolactone,
α, α-diallyl-β-butyrolactone,
α, α-dibenzyl-β-butyrolactone,
α, α-diphenethyl-β-butyrolactone,
β-butyrolactone derivatives such as α, α-difluoro-β-butyrolactone;

α-methyl-γ-butyrolactone,
α-ethyl-γ-butyrolactone,
α-propyl-γ-butyrolactone,
α-vinyl-γ-butyrolactone,
α-allyl-γ-butyrolactone,
α-phenyl-γ-butyrolactone,
α-tolyl-γ-butyrolactone,
α-naphthyl-γ-butyrolactone,
α-fluoro-γ-butyrolactone,
α, α-dimethyl-γ-butyrolactone,
α, α-diethyl-γ-butyrolactone,
α-ethyl-α-methyl-γ-butyrolactone,
α-methyl-α-phenyl-γ-butyrolactone,
α, α-diphenyl-γ-butyrolactone,
α, α-ditolyl-γ-butyrolactone,
α, α-bis (dimethylphenyl) -γ-butyrolactone,
α, α-dinaphthyl-γ-butyrolactone,
α, α-divinyl-γ-butyrolactone,
α, α-diallyl-γ-butyrolactone,
α, α-dibenzyl-γ-butyrolactone,
α, α-diphenethyl-γ-butyrolactone,
γ-butyrolactone derivatives such as α, α-difluoro-γ-butyrolactone;

α-methyl-γ-valerolactone,
α-ethyl-γ-valerolactone,
α-propyl-γ-valerolactone,
α-vinyl-γ-valerolactone,
α-allyl-γ-valerolactone,
α-phenyl-γ-valerolactone,
α-tolyl-γ-valerolactone,
α-naphthyl-γ-valerolactone,
α-fluoro-γ-valerolactone,
α, α-dimethyl-γ-valerolactone,
α, α-diethyl-γ-valerolactone,
α-ethyl-α-methyl-γ-valerolactone,
α-methyl-α-phenyl-γ-valerolactone,
α, α-diphenyl-γ-valerolactone,
α, α-ditolyl-γ-valerolactone,
α, α-bis (dimethylphenyl) -γ-valerolactone,
α, α-dinaphthyl-γ-valerolactone,
α, α-divinyl-γ-valerolactone,
α, α-diallyl-γ-valerolactone,
α, α-dibenzyl-γ-valerolactone,
α, α-diphenethyl-γ-valerolactone,
γ-valerolactone derivatives such as α, α-difluoro-γ-valerolactone;

α-methyl-δ-valerolactone,
α-ethyl-δ-valerolactone,
α-propyl-δ-valerolactone,
α-vinyl-δ-valerolactone,
α-allyl-δ-valerolactone,
α-phenyl-δ-valerolactone,
α-tolyl-δ-valerolactone,
α-naphthyl-δ-valerolactone,
α-fluoro-δ-valerolactone,
α, α-dimethyl-δ-valerolactone,
α, α-diethyl-δ-valerolactone,
α-ethyl-α-methyl-δ-valerolactone,
α-methyl-α-phenyl-δ-valerolactone,
α, α-diphenyl-δ-valerolactone,
α, α-ditolyl-δ-valerolactone,
α, α-bis (dimethylphenyl) -δ-valerolactone,
α, α-dinaphthyl-δ-valerolactone,
α, α-divinyl-δ-valerolactone,
α, α-diallyl-δ-valerolactone,
α, α-dibenzyl-δ-valerolactone,
α, α-diphenethyl-δ-valerolactone,
δ-valerolactone derivatives such as α, α-difluoro-δ-valerolactone;

α-methyl-γ-caprolactone,
α-ethyl-γ-caprolactone,
α-propyl-γ-caprolactone,
α-vinyl-γ-caprolactone,
α-allyl-γ-caprolactone,
α-phenyl-γ-caprolactone,
α-tolyl-γ-caprolactone,
α-naphthyl-γ-caprolactone,
α-fluoro-γ-caprolactone,
α, α-dimethyl-γ-caprolactone,
α, α-diethyl-γ-caprolactone,
α-ethyl-α-methyl-γ-caprolactone,
α-methyl-α-phenyl-γ-caprolactone,
α, α-diphenyl-γ-caprolactone,
α, α-ditolyl-γ-caprolactone,
α, α-bis (dimethylphenyl) -γ-caprolactone,
α, α-dinaphthyl-γ-caprolactone,
α, α-divinyl-γ-caprolactone,
α, α-diallyl-γ-caprolactone,
α, α-dibenzyl-γ-caprolactone,
α, α-diphenethyl-γ-caprolactone,
γ-caprolactone derivatives such as α, α-difluoro-γ-caprolactone;

α-methyl-δ-caprolactone,
α-ethyl-δ-caprolactone,
α-propyl-δ-caprolactone,
α-vinyl-δ-caprolactone,
α-allyl-δ-caprolactone,
α-phenyl-δ-caprolactone,
α-tolyl-δ-caprolactone,
α-naphthyl-δ-caprolactone,
α-fluoro-δ-caprolactone,
α, α-dimethyl-δ-caprolactone,
α, α-diethyl-δ-caprolactone,
α-ethyl-α-methyl-δ-caprolactone,
α-methyl-α-phenyl-δ-caprolactone,
α, α-diphenyl-δ-caprolactone,
α, α-ditolyl-δ-caprolactone,
α, α-bis (dimethylphenyl) -δ-caprolactone,
α, α-dinaphthyl-δ-caprolactone,
α, α-divinyl-δ-caprolactone,
α, α-diallyl-δ-caprolactone,
α, α-dibenzyl-δ-caprolactone,
α, α-diphenethyl-δ-caprolactone,
δ-caprolactone derivatives such as α, α-difluoro-δ-caprolactone;

α-methyl-ε-caprolactone,
α-ethyl-ε-caprolactone,
α-propyl-ε-caprolactone,
α-vinyl-ε-caprolactone,
α-allyl-ε-caprolactone,
α-phenyl-ε-caprolactone,
α-tolyl-ε-caprolactone,
α-naphthyl-ε-caprolactone,
α-fluoro-ε-caprolactone,
α, α-dimethyl-ε-caprolactone,
α, α-diethyl-ε-caprolactone,
α-ethyl-α-methyl-ε-caprolactone,
α-methyl-α-phenyl-ε-caprolactone,
α, α-diphenyl-ε-caprolactone,
α, α-ditolyl-ε-caprolactone,
α, α-bis (dimethylphenyl) -ε-caprolactone,
α, α-dinaphthyl-ε-caprolactone,
α, α-divinyl-ε-caprolactone,
α, α-diallyl-ε-caprolactone,
α, α-dibenzyl-ε-caprolactone,
α, α-diphenethyl-ε-caprolactone,
ε-caprolactone derivatives such as α, α-difluoro-ε-caprolactone, etc.

Among these,
α-methyl-γ-butyrolactone,
α-methyl-γ-valerolactone,
α-methyl-δ-valerolactone,
α-methyl substituted lactones such as α-methyl-δ-caprolactone;
α-phenyl-γ-butyrolactone,
α-phenyl-γ-valerolactone,
α-phenyl-δ-valerolactone,
α-phenyl substituted lactones such as α-phenyl-δ-caprolactone;
α, α-dimethyl-γ-butyrolactone,
α, α-dimethyl-γ-valerolactone,
α, α-dimethyl-δ-valerolactone,
α, α-dimethyl-γ-caprolactone,
α, α-dimethyl-substituted lactones such as α, α-dimethyl-δ-caprolactone;
α, α-diphenyl-γ-butyrolactone,
α, α-diphenyl-γ-valerolactone,
α, α-diphenyl-δ-valerolactone,
α, α-diphenyl-γ-caprolactone,
α, α-diphenyl-substituted lactones such as α, α-diphenyl-δ-caprolactone are preferred.

Among these,
α-methyl-γ-butyrolactone,
α-phenyl-γ-butyrolactone,
α, α-dimethyl-γ-butyrolactone,
α, α-diphenyl-γ-butyrolactone and the like are more preferable.

<1-2-10. Compound having carbon-carbon triple bond>
The compound having a carbon-carbon triple bond is not particularly limited as long as it is a compound having a carbon-carbon triple bond in the molecule.

Specific examples of the compound having a carbon-carbon triple bond include, for example,
2-propynylmethyl carbonate,
2-propynyl ethyl carbonate,
2-propynylpropyl carbonate,
2-propynyl butyl carbonate,
2-propynyl cyclohexyl carbonate,
2-propynylphenyl carbonate,
Bis-2-propynyl carbonate,
2-butynylmethyl carbonate,
2-butynyl ethyl carbonate,
2-butynylpropyl carbonate,
2-butynyl butyl carbonate,
2-butynyl cyclohexyl carbonate 2-butynyl phenyl carbonate bis 2-butynyl carbonate,
3-butynylmethyl carbonate,
3-butynyl ethyl carbonate,
2-pentynyl methyl carbonate,
1-methyl-2-butynylmethyl carbonate,
2-butyne-1,4-diol dimethyl carbonate,
2-butyne-1,4-diol diethyl carbonate,
2-butyne-1,4-diol dipropyl carbonate,
Carbonate compounds such as 2-butyne-1,4-diol dicyclohexyl carbonate 2-butyne-1,4-diol diphenyl carbonate;

2-propynyl acetate,
2-propynyl propionate,
2-propynyl butyrate,
2-propynyl cyclohexanecarboxylic acid,
2-propynyl benzoate,
2-butynyl acetate,
2-butynyl propionate 2-butynylbutyrate 2-butynylcyclohexanecarboxylate 2-butynyl,
2-butynyl benzoate,
3-butynyl acetate,
3-butynyl propionate,
3-butynyl butyrate,
3-butynyl cyclohexanecarboxylate,
3-butynyl benzoate,
2-pentynyl acetate,
1-methyl-2-butynyl acetate,
2-butyne-1,4-diol diacetate,
2-butyne-1,4-diol dipropionate,
2-butyne-1,4-diol dicyclohexanecarboxylate,
Carboxylate compounds such as 2-butyne-1,4-diol dibenzoate;

2-propynyl methanesulfonate,
2-propynyl ethanesulfonate,
2-propynyl propanesulfonate,
Cyclohexanesulfonic acid 2-propynylbenzenesulfonic acid 2-propynyl,
2-butynyl methanesulfonate,
2-butynyl ethanesulfonate,
2-butynyl propanesulfonate,
2-butynyl benzenesulfonate 2-butynyl benzenesulfonate,
3-butynyl methanesulfonate,
3-butynyl ethanesulfonate,
3-butynyl propanesulfonate,
3-butynyl benzenesulfonate 3-butynyl benzenesulfonate,
2-pentynyl methanesulfonate,
1-methyl-2-butynyl methanesulfonate,
2-propynyl trifluoromethanesulfonate,
2-propynyl pentafluoroethanesulfonate,
2-butyne-1,4-diol dimethanesulfonate,
2-butyne-1,4-diol dipropanesulfonate,
Examples include 2-butyne-1,4-diol dicyclohexanesulfonate, sulfonic acid ester compounds such as 2-butyne-1,4-diol dibenzenesulfonate, and the like.

<1-2-11. Content, technical scope, etc.>
These “compounds of the present invention”, that is, compounds represented by the general formula (1), nitrile compounds, isocyanate compounds, phosphazene compounds, disulfonic acid ester compounds, sulfide compounds, disulfide compounds, acid anhydrides, substituted at the α-position At least one compound selected from the group consisting of a lactone compound having a group and a compound having a carbon-carbon triple bond may be used alone, or two or more compounds may be used in any combination and ratio. You may use together. In the “compound of the present invention”, among the compounds classified as above, one kind may be used alone, or two or more kinds of compounds may be used in any combination and ratio. Good.

  The content ratio of these “compounds of the present invention” in the non-aqueous electrolyte solution is not particularly limited, but is generally 0.001% by mass or more, more preferably 0.01% or more in total with respect to the entire non-aqueous electrolyte solution. It is at least 0.1% by mass, more preferably at least 0.1% by mass. Further, the upper limit is 50% by mass or less in total, more preferably 25% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. If the concentration of the “compound of the present invention” is too low, it may be difficult to obtain the effect of improving the continuous charge characteristics. On the other hand, if the concentration is too high, the charge / discharge efficiency may be reduced.

<1-3. Non-aqueous solvent>
The non-aqueous solvent contained in the non-aqueous electrolyte of the present invention is not particularly limited as long as it is a non-aqueous solvent that does not adversely affect battery characteristics when used as a battery. It is preferable that it is 1 or more types in the non-aqueous solvent used for the non-aqueous electrolyte solution hung up below.

As an example of the non-aqueous solvent used, for example,
Chain or cyclic carbonate,
Chain or cyclic carboxylic acid ester,
Chain and cyclic ethers,
And sulfur-containing organic solvents.

Moreover, although there is no restriction | limiting in the kind of chain carbonate, Dialkyl carbonate is preferable and carbon number of the alkyl group which comprises is each preferable 1-5, Most preferably, it is 1-4. As a specific example, for example,
Dimethyl carbonate,
Ethyl methyl carbonate,
Diethyl carbonate,
Methyl-n-propyl carbonate,
Ethyl-n-propyl carbonate,
Examples include di-n-propyl carbonate.

  Among these, dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate is preferable in terms of industrial availability and various characteristics in the non-aqueous electrolyte secondary battery.

Although there is no restriction | limiting in the kind of cyclic carbonate, As for carbon number of the alkylene group which comprises a cyclic carbonate, 2-6 are preferable, Most preferably, it is 2-4. Specifically, for example,
Ethylene carbonate,
Propylene carbonate,
Examples include butylene carbonate (2-ethylethylene carbonate, cis and trans 2,3-dimethylethylene carbonate).

  Among these, ethylene carbonate or propylene carbonate is preferable in that various characteristics in the non-aqueous electrolyte secondary battery are good.

Furthermore, the type of the chain carboxylic acid ester is not limited, but as a specific example, for example,
Methyl acetate,
Ethyl acetate,
Acetic acid-n-propyl,
Acetic acid-iso-propyl,
N-butyl acetate,
Acetate-iso-butyl acetate,
Acetate-tert-butyl acetate,
Methyl propionate,
Ethyl propionate,
N-propyl propionate,
Propionic acid-iso-propyl,
Propionate-n-butyl,
Propionate-iso-butyl,
And propionic acid-tert-butyl.

  Among these, ethyl acetate, methyl propionate, or ethyl propionate is preferable in terms of industrial availability and various characteristics in the non-aqueous electrolyte secondary battery.

  Also, the type of cyclic carboxylic acid ester is not limited, but examples of commonly used ones include γ-butyrolactone, γ-valerolactone, δ-valerolactone, and the like.

  Among these, γ-butyrolactone is preferable in terms of industrial availability and various characteristics in the non-aqueous electrolyte secondary battery.

Furthermore, there is no restriction | limiting also in the kind of chain ether, As a specific example, for example,
Dimethoxymethane,
Dimethoxyethane,
Diethoxymethane,
Diethoxyethane,
Ethoxymethoxymethane,
Examples include ethoxymethoxyethane.

  Among these, dimethoxyethane and diethoxyethane are preferable in terms of industrial availability and various characteristics in the non-aqueous electrolyte secondary battery.

In addition, the type of cyclic ether is not limited, and specific examples include, for example,
Tetrahydrofuran,
2-methyltetrahydrofuran,
Tetrahydropyran etc. are mentioned.

In addition, the type of sulfur-containing organic solvent is not particularly limited, but as a specific example, for example,
Ethylene sulfite,
1,3-propane sultone,
1,4-butane sultone,
Methyl methanesulfonate,
Sulfolane,
Sulfolene,
Etc.

  Among these, a chain or cyclic carbonate or a chain or cyclic carboxylic acid ester is preferable in terms of various characteristics in the non-aqueous electrolyte secondary battery, and among them, ethylene carbonate, propylene carbonate, dimethyl carbonate, More preferred is ethyl methyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate or γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate or γ- Butyrolactone is more preferred

  These may be used alone or in combination of two or more, but it is preferable to use two or more compounds in combination. For example, it is particularly preferable to use a high dielectric constant solvent of cyclic carbonates in combination with a low viscosity solvent such as chain carbonates or chain esters.

  One preferred combination of non-aqueous solvents is a combination mainly composed of cyclic carbonates and chain carbonates. Among them, the total of the cyclic carbonates and the chain carbonates in the entire non-aqueous solvent is usually 80% by volume or more, preferably 85% by volume or more, and more preferably 90% by volume or more. The volume of the cyclic carbonates relative to the total of the cyclic carbonates and the chain carbonates is preferably 5% by volume or more, more preferably 10% by volume or more, particularly preferably 15% by volume or more, and usually 50% by volume. Hereinafter, it is preferably 35% by volume or less, more preferably 30% or less. Use of a combination of these non-aqueous solvents is preferable because the balance between cycle characteristics and high-temperature storage characteristics (particularly, remaining capacity and high-load discharge capacity after high-temperature storage) of a battery produced using the non-aqueous solvent is improved.

  Specific examples of preferred combinations of the above cyclic carbonates and chain carbonates include, for example, ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate and diethyl carbonate, Examples thereof include ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.

  A combination in which propylene carbonate is further added to the combination of these ethylene carbonates and chain carbonates is also a preferable combination. In the case of containing propylene carbonate, the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, particularly preferably 95: 5 to 50:50. Furthermore, the amount of propylene carbonate in the entire non-aqueous solvent is 0.1% by volume or more, preferably 1% by volume or more, more preferably 2% by volume or more, usually 10% by volume or less, preferably 8% by volume or less, more Preferably, it is preferably 5% by volume or less because the discharge load is further excellent while maintaining the characteristics of the combination of ethylene carbonate and chain carbonates.

  Among these, those containing asymmetric chain carbonates are more preferable, especially ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl. Those containing ethylene carbonate such as methyl carbonate, symmetric chain carbonates and asymmetric chain carbonates, or further containing propylene carbonate are preferred because the balance between cycle characteristics and discharge load is good. Among these, those in which the asymmetric chain carbonate is ethyl methyl carbonate are preferable, and the number of carbon atoms of the alkyl group constituting the dialkyl carbonate is preferably 1 or 2.

  Another example of a preferable mixed solvent is one containing a chain ester. In particular, those containing a chain ester in the mixed solvent of cyclic carbonates and chain carbonates are preferable from the viewpoint of improving the discharge load of the battery. Examples of the chain esters include methyl acetate, ethyl acetate or propionic acid. Methyl is particularly preferred. The capacity of the chain ester in the entire non-aqueous solvent is usually 5% or more, preferably 8% or more, more preferably 15% or more, and usually 50% or less, preferably 35% or less, more preferably 30% or less. More preferably, it is 25% or less.

  Examples of other preferable non-aqueous solvents include one organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, γ-butyrolactone and γ-valerolactone, or two or more selected from the group A mixed solvent composed of an organic solvent occupies 60% by volume or more of the whole. Such a mixed solvent preferably has a flash point of 50 ° C. or higher, and particularly preferably 70 ° C. or higher. A non-aqueous electrolyte using this solvent reduces evaporation of the solvent and leakage even when used at high temperatures. Among them, the total of ethylene carbonate and γ-butyrolactone in the whole non-aqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate and γ-butyrolactone is 5:95 to 45%. : 55, or the total of ethylene carbonate and propylene carbonate is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate to propylene carbonate is 30:70 to 80:20. In general, the balance between cycle characteristics and discharge load characteristics is improved.

<1-4. Monofluorophosphate, Difluorophosphate>
The nonaqueous electrolytic solution of the present invention contains a monofluorophosphate and / or a difluorophosphate as an essential component. The “monofluorophosphate and / or difluorophosphate” used in the present invention is classified into its kind as long as it is formed from one or more monofluorophosphate ions and / or difluorophosphate ions and cations. Although there is no particular limitation, since the non-aqueous electrolyte to be finally produced needs to be usable as the electrolyte of the non-aqueous electrolyte secondary battery to be used, it needs to be selected in view of this. is there.

  Therefore, the monofluorophosphate and difluorophosphate in the present invention are selected from one or more monofluorophosphate ions, difluorophosphate ions, and Groups 1, 2, and 13 of the periodic table. And a salt with one or more metal ions (hereinafter abbreviated as “specific metal” where appropriate) or a salt with quaternary onium. Monofluorophosphate and / or difluorophosphate may be used alone or in any combination of two or more.

<1-4-1. Monofluorophosphoric acid metal salt, difluorophosphoric acid metal salt>
First, monofluorophosphate and difluorophosphate in the present invention are monofluorophosphate ions, salts of difluorophosphate ions and specific metal ions (hereinafter referred to as “monofluorophosphate metal salts” and “difluoro, respectively”, respectively). The case of “metal phosphate” may be abbreviated).

  Among the specific metals used in the monofluorophosphate metal salt and difluorophosphate metal salt in the present invention, specific examples of Group 1 metals in the periodic table include lithium, sodium, potassium, cesium and the like. Among these, lithium or sodium is preferable, and lithium is particularly preferable.

  Specific examples of Group 2 metals in the periodic table include magnesium, calcium, strontium, barium and the like. Among these, magnesium or calcium is preferable, and magnesium is particularly preferable.

  Specific examples of the group 13 metal in the periodic table include aluminum, gallium, indium, and thallium. Of these, aluminum or gallium is preferable, and aluminum is particularly preferable.

  The number of atoms of these specific metals that the monofluorophosphoric acid metal salt and difluorophosphoric acid metal salt in the present invention have in one molecule is not limited and may be only one atom or two or more atoms. Also good.

  When the monofluorophosphate metal salt or difluorophosphate metal salt in the present invention contains two or more specific metals in one molecule, the types of these specific metal atoms may be the same or different from each other. May be. Moreover, you may have 1 or 2 or more metal atoms other than a specific metal other than a specific metal.

Specific examples of the monofluorophosphoric acid metal salt and the difluorophosphoric acid metal salt include Li ₂ PO ₃ F, Na ₂ PO ₃ F, MgPO ₃ F, CaPO ₃ F, Al ₂ (PO ₃ F) ₃ , and Ga ₂ ( PO ₃ F) ₃ , LiPO ₂ F ₂ , NaPO ₂ F ₂ , Mg (PO ₂ F ₂ ) ₂ , Ca (PO ₂ F ₂ ) ₂ , Al (PO ₂ F ₂ ) ₃ , Ga (PO ₂ F ₂ ) ₃ etc. are mentioned. Among them, Li ₂ PO ₃ F, LiPO ₂ F ₂ , NaPO ₂ F ₂ , Mg (PO ₂ F ₂ ) _{2 and the} like are preferable.

<1-3-2. Monofluorophosphoric acid quaternary onium salt, difluorophosphoric acid quaternary onium salt>
Next, the monofluorophosphate and difluorophosphate in the present invention are monofluorophosphate ions, difluorophosphate ions and quaternary onium salts (hereinafter referred to as “monofluorophosphate quaternary onium salts”, The case of “difluorophosphoric acid quaternary onium salt” may be abbreviated).

  The quaternary onium used in the monofluorophosphoric acid quaternary onium salt and difluorophosphoric acid quaternary onium salt in the present invention is usually a cation, specifically, a cation represented by the following general formula (4). It is done.

In the general formula (4), R ^{4 to} R ⁷ each independently represents a hydrocarbon group. The kind of hydrocarbon group is not limited. That is, it may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a hydrocarbon group to which those groups are bonded. In the case of an aliphatic hydrocarbon group, it may be a chain or a ring, and may have a structure in which a chain and a ring are combined. In the case of a chain hydrocarbon group, it may be linear or branched. Moreover, it may be a saturated hydrocarbon group and may have an unsaturated bond.

Specific examples of the hydrocarbon group for R ^{4 to} R ⁷ include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Specific examples of the alkyl group include, for example,
Methyl group,
Ethyl group,
1-propyl group,
1-methylethyl group,
1-butyl group,
1-methylpropyl group,
2-methylpropyl group,
Examples include 1,1-dimethylethyl group.
Of these, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group and the like are preferable.

Specific examples of the cycloalkyl group include, for example,
A cyclopentyl group,
2-methylcyclopentyl group,
3-methylcyclopentyl group,
2,2-dimethylcyclopentyl group,
2,3-dimethylcyclopentyl group,
2,4-dimethylcyclopentyl group,
2,5-dimethylcyclopentyl group,
3,3-dimethylcyclopentyl group,
3,4-dimethylcyclopentyl group,
2-ethylcyclopentyl group,
3-ethylcyclopentyl group,
A cyclohexyl group,
2-methylcyclohexyl group,
3-methylcyclohexyl group,
4-methylcyclohexyl group,
2,2-dimethylcyclohexyl group,
2,3-dimethylcyclohexyl group,
2,4-dimethylcyclohexyl group,
2,5-dimethylcyclohexyl group,
2,6-dimethylcyclohexyl group,
3,4-dimethylcyclohexyl group,
3,5-dimethylcyclohexyl group,
2-ethylcyclohexyl group,
3-ethylcyclohexyl group,
4-ethylcyclohexyl group,
A bicyclo [3,2,1] oct-1-yl group,
And bicyclo [3,2,1] oct-2-yl group.

  Of these, a cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group and the like are preferable.

Specific examples of the aryl group include, for example,
Phenyl group,
2-methylphenyl group,
3-methylphenyl group,
4-methylphenyl group,
Examples include 2,3-dimethylphenyl group.
Of these, a phenyl group is preferred.

Specific examples of the aralkyl group include, for example,
Phenylmethyl group,
1-phenylethyl group,
2-phenylethyl group,
Diphenylmethyl group,
A triphenylmethyl group etc. are mentioned.
Of these, a phenylmethyl group and a 2-phenylethyl group are preferable.

The hydrocarbon group of R ^{4 to} R ⁷ may be substituted with one or more substituents. The type of the substituent is not limited as long as the effects in the present invention are not significantly impaired. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, an ether group, and an aldehyde group. It is done. In the case where the hydrocarbon group of R ⁴ to R ⁷ has two or more substituents, these substituents may be the same or may be different from one another.

The hydrocarbon groups of R ^{4 to} R ⁷ may be the same as or different from each other when any two or more are compared. When the hydrocarbon groups of R ^{4 to} R ⁷ have a substituent, the substituted hydrocarbon groups including those substituents may be the same as or different from each other. Further, any two or more of the hydrocarbon groups of R ^{4 to} R ⁷ may be bonded to each other to form a cyclic structure.

The carbon number of the hydrocarbon group of R ^{4 to} R ⁷ is usually 1 or more, and the upper limit is usually 20 or less, preferably 10 or less, more preferably 5 or less. When the amount is too large, the number of moles per mass decreases, and various effects tend to decrease. In addition, when the hydrocarbon group of R < ⁴ > -R < ⁷ > has a substituent, carbon number of the substituted hydrocarbon group also including those substituents shall satisfy | fill the said range.

  In the general formula (4), Q represents an atom belonging to Group 15 of the periodic table. Among these, a nitrogen atom or a phosphorus atom is preferable.

  From the above, preferable examples of the quaternary onium represented by the general formula (4) include aliphatic chain quaternary salts, aliphatic cyclic ammoniums, aliphatic cyclic phosphoniums, nitrogen-containing heterocyclic aromatic cations, and the like. Can be mentioned.

  As the aliphatic chain quaternary salt, tetraalkylammonium, tetraalkylphosphonium and the like are particularly preferable.

Specific examples of tetraalkylammonium include, for example,
Tetramethylammonium,
Ethyltrimethylammonium,
Diethyldimethylammonium,
Triethylmethylammonium,
Tetraethylammonium,
Examples include tetra-n-butylammonium.

Specific examples of tetraalkylphosphonium include, for example,
Tetramethylphosphonium,
Ethyl trimethylphosphonium,
Diethyldimethylphosphonium,
Triethylmethylphosphonium,
Tetraethylphosphonium,
Examples include tetra-n-butylphosphonium.

  As the aliphatic cyclic ammonium, pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, piperidiniums and the like are particularly preferable.

Specific examples of pyrrolidiniums include, for example,
N, N-dimethylpyrrolidinium,
N-ethyl-N-methylpyrrolidinium,
N, N-diethylpyrrolidinium and the like can be mentioned.

Specific examples of morpholiniums include, for example,
N, N-dimethylmorpholinium,
N-ethyl-N-methylmorpholinium,
N, N-diethylmorpholinium and the like can be mentioned.

As specific examples of imidazolinium, for example,
N, N′-dimethylimidazolinium,
N-ethyl-N′-methylimidazolinium,
N, N′-diethylimidazolinium,
1,2,3-trimethylimidazolinium and the like.

Specific examples of tetrahydropyrimidiniums include, for example:
N, N′-dimethyltetrahydropyrimidinium,
N-ethyl-N′-methyltetrahydropyrimidinium,
N, N′-diethyltetrahydropyrimidinium,
1,2,3-trimethyltetrahydropyrimidinium and the like.

Specific examples of piperaziniums include, for example,
N, N, N ′, N′-tetramethylpiperazinium,
N-ethyl-N, N ′, N′-trimethylpiperazinium,
N, N-diethyl-N ′, N′-dimethylpiperazinium,
N, N, N′-triethyl-N′-methylpiperazinium,
N, N, N ′, N′-tetraethylpiperazinium and the like can be mentioned.

Specific examples of piperidiniums include, for example,
N, N-dimethylpiperidinium,
N-ethyl-N-methylpiperidinium,
N, N-diethylpiperidinium and the like can be mentioned.

  As the nitrogen-containing heterocyclic aromatic cation, pyridiniums, imidazoliums and the like are particularly preferable.

As specific examples of pyridiniums, for example,
N-methylpyridinium,
N-ethylpyridinium,
1,2-dimethylpyrimidinium,
1,3-dimethylpyrimidinium,
1,4-dimethylpyrimidinium,
Examples include 1-ethyl-2-methylpyrimidinium.

Specific examples of imidazoliums include, for example,
N, N′-dimethylimidazolium,
N-ethyl-N′-methylimidazolium,
N, N′-diethylimidazolium,
1,2,3-trimethylimidazolium and the like can be mentioned.

  That is, preferred examples of the monofluorophosphate quaternary onium salt and the difluorophosphate quaternary onium salt in the present invention are salts of the quaternary oniums exemplified above with monofluorophosphate ions and / or difluorophosphate ions. become.

<1-4-3. Content, detection (origin of content), technical scope, etc.>
In the non-aqueous electrolyte of the present invention, one type of monofluorophosphate or difluorophosphate may be used, and two or more types of monofluorophosphate and / or difluorophosphate may be used in any combination and You may use together by a ratio.

  Moreover, there is no restriction | limiting in the molecular weight of a monofluorophosphate and a difluorophosphate, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually, it is 100 or more. Moreover, although there is no restriction | limiting in particular in an upper limit, In view of the reactivity of this reaction, 1000 or less normally, Preferably 500 or less is practical and preferable.

  The ratio of monofluorophosphate and difluorophosphate in the non-aqueous electrolyte is preferably 10 ppm or more (0.001% by mass or more) in total, more preferably with respect to the whole non-aqueous electrolyte. It is 0.01 mass% or more, Especially preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. Further, the upper limit is the sum of them, preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less. If the concentration of monofluorophosphate or difluorophosphate is too low, it may be difficult to suppress gas generation during continuous charging and improve battery characteristics. On the other hand, if the concentration is too high, the charge / discharge efficiency will decrease. May be invited.

  When the monofluorophosphate and difluorophosphate are actually used as a non-aqueous electrolyte for the preparation of a non-aqueous electrolyte secondary battery, even if the battery is disassembled and the non-aqueous electrolyte is taken out again, The content is often significantly reduced. Accordingly, it is considered that the present invention includes those in which at least one monofluorophosphate and / or difluorophosphate can be detected even in a small amount from the non-aqueous electrolyte extracted from the battery. In addition, when monofluorophosphate and difluorophosphate are actually used as a non-aqueous electrolyte for the production of a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte obtained by disassembling the battery and taking it out again is monofluoro electrolyte. Even when the phosphate and / or difluorophosphate is not contained, it is often detected on the positive electrode, the negative electrode or the separator, which are other components of the non-aqueous electrolyte secondary battery. Accordingly, the present invention also includes a case where at least one monofluorophosphate and / or difluorophosphate is detected from at least one component of the positive electrode, the negative electrode, and the separator.

  In addition, the present invention includes a case where monofluorophosphate and / or difluorophosphate is contained in the nonaqueous electrolytic solution and used in at least one constituent member of the positive electrode, the negative electrode, and the separator. Is considered.

  On the other hand, monofluorophosphate and / or difluorophosphate may be contained in advance in the positive electrode of the nonaqueous electrolyte secondary battery to be produced or on the surface of the positive electrode. In this case, it is expected that a part or all of the monofluorophosphate and / or difluorophosphate contained in advance is dissolved in the non-aqueous electrolyte and expresses the function, and this case is also included in the present invention. Is considered to be.

  There are no particular limitations on the means for pre-contained in the positive electrode or on the surface of the positive electrode, but specific examples include dissolving monofluorophosphate and / or difluorophosphate in a slurry to be prepared at the time of preparing the positive electrode, which will be described later. Or, after applying or impregnating a solution prepared by dissolving monofluorophosphate and / or difluorophosphate in an arbitrary non-aqueous solvent in advance to the positive electrode already prepared, the used solvent is dried. The method of making it contain by removing is mentioned.

  Further, when a non-aqueous electrolyte secondary battery is actually produced, the non-aqueous electrolyte containing at least one monofluorophosphate and / or difluorophosphate may be contained in the positive electrode or on the positive electrode surface. . When producing a non-aqueous electrolyte secondary battery, since the non-aqueous electrolyte is impregnated in the positive electrode, monofluorophosphate and difluorophosphate are often contained in the positive electrode or on the surface of the positive electrode. Therefore, what can detect at least monofluorophosphate and / or difluorophosphate from the positive electrode collected when the battery is disassembled is considered to be included in the present invention.

  Moreover, the monofluorophosphate and the difluorophosphate may be previously contained in the negative electrode or the surface of the negative electrode of the produced nonaqueous electrolyte secondary battery. In this case, it is expected that a part or all of the monofluorophosphate and / or difluorophosphate contained in advance is dissolved in the non-aqueous electrolyte and expresses the function, and is included in the present invention. It is regarded. There are no particular restrictions on the means for inclusion in the negative electrode or the surface of the negative electrode in advance, but as a specific example, monofluorophosphate and difluorophosphate are dissolved in a slurry to be prepared at the time of preparing the negative electrode, which will be described later. Or, after applying or impregnating a solution prepared by dissolving monofluorophosphate and difluorophosphate in an arbitrary non-aqueous solvent to the negative electrode already prepared, the used solvent is dried and removed. The method of making it contain etc. is mentioned.

  Further, when a non-aqueous electrolyte secondary battery is actually produced, it may be contained in the negative electrode or on the negative electrode surface from a non-aqueous electrolyte containing at least one monofluorophosphate and difluorophosphate. When producing a secondary battery, since the nonaqueous electrolyte is impregnated in the negative electrode, monofluorophosphate and difluorophosphate are often contained in the negative electrode or on the negative electrode surface. Therefore, what can detect at least monofluorophosphate and difluorophosphate from the negative electrode collected when the battery is disassembled is considered to be included in the present invention.

  Furthermore, the monofluorophosphate and / or difluorophosphate may be preliminarily contained in the separator of the non-aqueous electrolyte secondary battery to be produced or on the surface of the separator. In this case, a part or all of the monofluorophosphate and difluorophosphate contained in advance is expected to be dissolved in the non-aqueous electrolyte and to exhibit a function, and is considered to be included in the present invention. . The means for containing in the separator or on the surface of the separator in advance is not particularly limited. As a specific example, a monofluorophosphate and a difluorophosphate are mixed at the time of producing the separator, or a non-aqueous electrolyte solution is used. After applying or impregnating a solution prepared by pre-dissolving monofluorophosphate and difluorophosphate in any non-aqueous solvent to the separator before making the secondary battery, the used solvent is dried and removed. The method of making it contain by doing is mentioned.

  Further, when a non-aqueous electrolyte secondary battery is actually produced, the non-aqueous electrolyte containing monofluorophosphate and / or difluorophosphate may be contained in the separator or on the separator surface. When producing a non-aqueous electrolyte secondary battery, since the separator is impregnated with the non-aqueous electrolyte, monofluorophosphate and difluorophosphate are often contained in the separator or on the separator surface. Therefore, what can detect at least monofluorophosphate and difluorophosphate from the separator collected when the battery is disassembled is considered to be included in the present invention.

<1-5. Additives>
The nonaqueous electrolytic solution of the present invention may contain various additives as long as the effects of the present invention are not significantly impaired. In the case where the preparation process is performed by adding an additive, a conventionally known one can be arbitrarily used. In addition, an additive may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the additive include an overcharge inhibitor and an auxiliary agent for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage. Among these, carbonates having at least one of an unsaturated bond and a halogen atom as an aid for improving capacity retention characteristics and cycle characteristics after high-temperature storage (hereinafter sometimes abbreviated as “specific carbonate”) Is preferably added. Hereinafter, the specific carbonate and other additives will be described separately.

<1-5-1. Specific carbonate>
The specific carbonate is a carbonate having at least one of an unsaturated bond and a halogen atom. However, the specific carbonate may have only an unsaturated bond, may have only a halogen atom, and is unsaturated. It may have both a bond and a halogen atom.

  There is no restriction | limiting in particular in the molecular weight of a specific carbonate, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually, 50 or more, Preferably it is 80 or more, Usually, 250 or less, Preferably it is 150 or less. If the molecular weight is too large, the solubility of the specific carbonate in the non-aqueous electrolytic solution may be reduced, and the effect may not be sufficiently exhibited.

  Moreover, there is no restriction | limiting in particular also in the manufacturing method of a specific carbonate, It is possible to select and manufacture a well-known method arbitrarily.

  In addition, the specific carbonate may be included alone in the nonaqueous electrolytic solution of the present invention, or two or more may be combined in any combination and ratio.

  Moreover, there is no restriction | limiting in the compounding quantity of the specific carbonate with respect to the non-aqueous electrolyte solution of this invention, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually 0.01 mass with respect to the non-aqueous electrolyte solution of this invention. %, Preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and usually 70% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. Is desirable. In particular, the carbonate having an unsaturated bond is preferably contained at 10% by mass or less with respect to the non-aqueous electrolyte solution.

  Below the lower limit of this range, when the non-aqueous electrolyte solution of the present invention is used in a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery is less likely to exhibit a sufficient cycle characteristic improving effect. There is. In addition, if the ratio of the specific carbonate is too large, when the non-aqueous electrolyte solution of the present invention is used in a non-aqueous electrolyte secondary battery, the high-temperature storage characteristics and continuous charge characteristics of the non-aqueous electrolyte secondary battery deteriorate. In particular, there are cases where the amount of gas generated increases and the capacity retention rate decreases.

<1-5-1-1. Unsaturated carbonate>
Among the specific carbonates according to the present invention, the carbonate having an unsaturated bond (hereinafter sometimes abbreviated as “unsaturated carbonate”) is not limited as long as it has a carbon-carbon double bond. Any unsaturated carbonate can be used. In addition, the carbonate which has an aromatic ring shall also be contained in the carbonate which has an unsaturated bond.

  Examples of unsaturated carbonates include vinylene carbonate derivatives, ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, phenyl carbonates, vinyl carbonates, allyl carbonates, and the like. .

  Specific examples of vinylene carbonate derivatives include vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, catechol carbonate and the like.

  Specific examples of the ethylene carbonate derivatives substituted with an aromatic ring or a substituent having a carbon-carbon unsaturated bond include vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, phenyl ethylene carbonate, 4,5-diphenyl ethylene carbonate. Etc.

  Specific examples of phenyl carbonates include diphenyl carbonate, ethyl phenyl carbonate, methyl phenyl carbonate, t-butyl phenyl carbonate, and the like.

  Specific examples of vinyl carbonates include divinyl carbonate and methyl vinyl carbonate.

  Specific examples of allyl carbonates include diallyl carbonate and allyl methyl carbonate.

  Among these unsaturated carbonates, as the specific carbonate, vinylene carbonate derivatives, ethylene derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond are preferable, and in particular, vinylene carbonate, 4,5- Diphenyl vinylene carbonate, 4,5-dimethyl vinylene carbonate or vinyl ethylene carbonate is more preferably used because it forms a stable interface protective film.

<1-5-1-2. Halogenated carbonate>
On the other hand, among the specific carbonates according to the present invention, the carbonate having a halogen atom (hereinafter sometimes abbreviated as “halogenated carbonate”) is not particularly limited as long as it is a carbonate having a halogen atom. Any halogenated carbonate can be used.

  Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable. The number of halogen atoms contained in the halogenated carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less. When the halogenated carbonate has a plurality of halogen atoms, they may be the same as or different from each other.

  Examples of halogenated carbonates include ethylene carbonate derivatives, dimethyl carbonate derivatives, ethyl methyl carbonate derivatives, diethyl carbonate derivatives and the like.

Specific examples of ethylene carbonate derivatives include, for example,
Fluoroethylene carbonate,
Chloroethylene carbonate,
4,4-difluoroethylene carbonate,
4,5-difluoroethylene carbonate,
4,4-dichloroethylene carbonate,
4,5-dichloroethylene carbonate,
4-fluoro-4-methylethylene carbonate,
4-chloro-4-methylethylene carbonate,
4,5-difluoro-4-methylethylene carbonate,
4,5-dichloro-4-methylethylene carbonate,
4-fluoro-5-methylethylene carbonate,
4-chloro-5-methylethylene carbonate,
4,4-difluoro-5-methylethylene carbonate,
4,4-dichloro-5-methylethylene carbonate,
4- (fluoromethyl) -ethylene carbonate,
4- (chloromethyl) -ethylene carbonate,
4- (difluoromethyl) -ethylene carbonate,
4- (dichloromethyl) -ethylene carbonate,
4- (trifluoromethyl) -ethylene carbonate,
4- (trichloromethyl) -ethylene carbonate,
4- (fluoromethyl) -4-fluoroethylene carbonate,
4- (chloromethyl) -4-chloroethylene carbonate,
4- (fluoromethyl) -5-fluoroethylene carbonate,
4- (chloromethyl) -5-chloroethylene carbonate,
4-fluoro-4,5-dimethylethylene carbonate,
4-chloro-4,5-dimethylethylene carbonate,
4,5-difluoro-4,5-dimethylethylene carbonate,
4,5-dichloro-4,5-dimethylethylene carbonate,
4,4-difluoro-5,5-dimethylethylene carbonate,
Examples include 4,4-dichloro-5,5-dimethylethylene carbonate.

Specific examples of dimethyl carbonate derivatives include, for example,
Fluoromethyl methyl carbonate,
Difluoromethyl methyl carbonate,
Trifluoromethyl methyl carbonate,
Bis (fluoromethyl) carbonate,
Bis (difluoromethyl) carbonate,
Bis (trifluoromethyl) carbonate,
Chloromethyl methyl carbonate,
Dichloromethyl methyl carbonate,
Trichloromethyl methyl carbonate,
Bis (chloromethyl) carbonate,
Bis (dichloromethyl) carbonate,
Bis (trichloromethyl) carbonate etc. are mentioned.

Specific examples of ethyl methyl carbonate derivatives include, for example,
2-fluoroethyl methyl carbonate,
Ethyl fluoromethyl carbonate,
2,2-difluoroethyl methyl carbonate,
2-fluoroethyl fluoromethyl carbonate,
Ethyl difluoromethyl carbonate,
2,2,2-trifluoroethyl methyl carbonate,
2,2-difluoroethyl fluoromethyl carbonate,
2-fluoroethyl difluoromethyl carbonate,
Ethyl trifluoromethyl carbonate,
2-chloroethyl methyl carbonate,
Ethyl chloromethyl carbonate,
2,2-dichloroethyl methyl carbonate,
2-chloroethyl chloromethyl carbonate,
Ethyl dichloromethyl carbonate,
2,2,2-trichloroethyl methyl carbonate,
2,2-dichloroethyl chloromethyl carbonate,
2-chloroethyl dichloromethyl carbonate,
Examples include ethyl trichloromethyl carbonate.

Specific examples of diethyl carbonate derivatives include, for example,
Ethyl- (2-fluoroethyl) carbonate,
Ethyl- (2,2-difluoroethyl) carbonate,
Bis (2-fluoroethyl) carbonate,
Ethyl- (2,2,2-trifluoroethyl) carbonate,
2,2-difluoroethyl-2′-fluoroethyl carbonate,
Bis (2,2-difluoroethyl) carbonate,
2,2,2-trifluoroethyl-2′-fluoroethyl carbonate,
2,2,2-trifluoroethyl-2 ′, 2′-difluoroethyl carbonate,
Bis (2,2,2-trifluoroethyl) carbonate,
Ethyl- (2-chloroethyl) carbonate,
Ethyl- (2,2-dichloroethyl) carbonate,
Bis (2-chloroethyl) carbonate,
Ethyl- (2,2,2-trichloroethyl) carbonate,
2,2-dichloroethyl-2'-chloroethyl carbonate,
Bis (2,2-dichloroethyl) carbonate,
2,2,2-trichloroethyl-2′-chloroethyl carbonate,
2,2,2-trichloroethyl-2 ′, 2′-dichloroethyl carbonate,
Examples thereof include bis (2,2,2-trichloroethyl) carbonate.

  Among these halogenated carbonates, carbonates having fluorine atoms are preferred, carbonate derivatives having fluorine atoms are more preferred, especially fluoroethylene carbonate, 4- (fluoromethyl) -ethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate is more preferably used because it forms an interface protective film.

<1-5-1-3. Halogenated unsaturated carbonate>
Furthermore, as the specific carbonate, a carbonate having both an unsaturated bond and a halogen atom (abbreviated as “halogenated unsaturated carbonate”) may be used. There is no restriction | limiting in particular as a halogenated unsaturated carbonate, As long as the effect of this invention is not impaired remarkably, arbitrary halogenated unsaturated carbonates can be used.

  Examples of the halogenated unsaturated carbonate include vinylene carbonate derivatives, ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, and allyl carbonates.

Specific examples of vinylene carbonate derivatives include, for example,
Fluorovinylene carbonate,
4-fluoro-5-methylvinylene carbonate,
4-fluoro-5-phenyl vinylene carbonate,
4- (trifluoromethyl) vinylene carbonate chlorovinylene carbonate,
4-chloro-5-methylvinylene carbonate,
4-chloro-5-phenyl vinylene carbonate 4- (trichloromethyl) vinylene carbonate, etc. are mentioned.

Specific examples of ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond include, for example,
4-fluoro-4-vinylethylene carbonate,
4-fluoro-5-vinylethylene carbonate,
4,4-difluoro-5-vinylethylene carbonate,
4,5-difluoro-4-vinylethylene carbonate,
4-chloro-5-vinylethylene carbonate,
4,4-dichloro-5-vinylethylene carbonate,
4,5-dichloro-4-vinylethylene carbonate,
4-fluoro-4,5-divinylethylene carbonate,
4,5-difluoro-4,5-divinylethylene carbonate,
4-chloro-4,5-divinylethylene carbonate,
4,5-dichloro-4,5-divinylethylene carbonate,
4-fluoro-4-phenylethylene carbonate,
4-fluoro-5-phenylethylene carbonate,
4,4-difluoro-5-phenylethylene carbonate,
4,5-difluoro-4-phenylethylene carbonate,
4-chloro-4-phenylethylene carbonate,
4-chloro-5-phenylethylene carbonate,
4,4-dichloro-5-phenylethylene carbonate,
4,5-dichloro-4-phenylethylene carbonate,
4,5-difluoro-4,5-diphenylethylene carbonate,
Examples include 4,5-dichloro-4,5-diphenylethylene carbonate.

Specific examples of phenyl carbonates include, for example,
Fluoromethylphenyl carbonate,
2-fluoroethyl phenyl carbonate,
2,2-difluoroethyl phenyl carbonate,
2,2,2-trifluoroethyl phenyl carbonate,
Chloromethylphenyl carbonate,
2-chloroethyl phenyl carbonate,
2,2-dichloroethyl phenyl carbonate,
Examples include 2,2,2-trichloroethyl phenyl carbonate.

Specific examples of vinyls include, for example,
Fluoromethyl vinyl carbonate,
2-fluoroethyl vinyl carbonate,
2,2-difluoroethyl vinyl carbonate,
2,2,2-trifluoroethyl vinyl carbonate,
Chloromethyl vinyl carbonate,
2-chloroethyl vinyl carbonate,
2,2-dichloroethyl vinyl carbonate,
Examples include 2,2,2-trichloroethyl vinyl carbonate.

Specific examples of allyl carbonates include, for example,
Fluoromethylallyl carbonate,
2-fluoroethyl allyl carbonate,
2,2-difluoroethyl allyl carbonate,
2,2,2-trifluoroethyl allyl carbonate,
Chloromethylallyl carbonate,
2-chloroethyl allyl carbonate,
2,2-dichloroethyl allyl carbonate,
Examples include 2,2,2-trichloroethyl allyl carbonate.

  Among the above-mentioned examples of the halogenated unsaturated carbonate, the specific carbonate has a high effect of improving cycle characteristics, “a group consisting of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, 4,5-difluoroethylene carbonate, and derivatives thereof. It is particularly preferable to use one or more compounds selected from In addition, these specific carbonates may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations. Moreover, when using together by arbitrary combinations, the compound of the same classification illustrated above may be used together, and you may use together by a compound of a different classification | category.

<1-5-2. Other additives>
Hereinafter, additives other than the specific carbonate will be described. Examples of additives other than the specific carbonate include overcharge inhibitors, auxiliary agents for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage, and the like.

<1-5-2-1. Overcharge prevention agent>
As a specific example of the overcharge inhibitor, for example,
Toluene derivatives such as toluene, xylene, etc .;
Biphenyl derivatives unsubstituted or substituted with alkyl groups, such as biphenyl, 2-methylbiphenyl, 3-methylbiphenyl 4-methylbiphenyl;
o-terphenyl, m-terphenyl, p-terphenyl and the like terphenyl derivatives unsubstituted or substituted with an alkyl group;
Partial hydrides of terphenyl derivatives that are unsubstituted or substituted with alkyl groups;
Cycloalkylbenzene derivatives such as cyclopentylbenzene and cyclohexylbenzene;
Alkylbenzene derivatives having a tertiary carbon directly bonded to a benzene ring such as cumene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene;
alkylbenzene derivatives having a quaternary carbon directly bonded to a benzene ring, such as t-butylbenzene, t-amylbenzene, t-hexylbenzene;
Aromatic compounds having an oxygen atom such as diphenyl ether and dibenzofuran;
Aromatic compounds such as

Furthermore, specific examples of other overcharge inhibitors include, for example,
A partially fluorinated product of the aromatic compound such as fluorobenzene, fluorotoluene, benzotrifluoride, 2-fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene;
Fluorine-containing anisole compounds such as 2,4-difluoroanisole, 2,5-difluoroanisole, 1,6-difluoroaniol;
And so on.

  In addition, these overcharge inhibitors may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations. Moreover, when using together by arbitrary combinations, the compound of the same classification illustrated above may be used together, and you may use together by a compound of a different classification | category.

Specific examples of using different types of compounds together include toluene derivatives and biphenyl derivatives;
Toluene derivatives and terphenyl derivatives;
Partial hydrides of toluene derivatives and terphenyl derivatives;
Toluene derivatives and cycloalkylbenzene derivatives;
An alkylbenzene derivative having a tertiary carbon bonded directly to a toluene derivative and a benzene ring;
An alkylbenzene derivative having a quaternary carbon directly bonded to a toluene derivative and a benzene ring;
An aromatic compound having a toluene derivative and an oxygen atom;
Partially fluorinated products of toluene derivatives and aromatic compounds;
A toluene derivative and a fluorine-containing anisole compound;

Biphenyl derivatives and terphenyl derivatives;
Partial hydrides of biphenyl and terphenyl derivatives;
Biphenyl derivatives and cycloalkylbenzene derivatives;
An alkylbenzene derivative having a tertiary carbon bonded directly to the benzene ring and the biphenyl derivative;
An alkylbenzene derivative having a quaternary carbon bonded directly to the biphenyl derivative and the benzene ring;
An aromatic compound having a biphenyl derivative and an oxygen atom;
Partially fluorinated products of biphenyl derivatives and aromatic compounds;
Biphenyl derivatives and fluorine-containing anisole compounds;

Terphenyl derivatives and partially hydrides of terphenyl derivatives;
Terphenyl derivatives and cycloalkylbenzene derivatives;
An alkylbenzene derivative having a tertiary carbon directly bonded to the terphenyl derivative and the benzene ring;
Alkylbenzene derivatives having a terphenyl derivative and a quaternary carbon bonded directly to the benzene ring;
A terphenyl derivative and an aromatic compound having an oxygen atom;
Partially fluorinated products of terphenyl derivatives and aromatic compounds;
Terphenyl derivatives and fluorine-containing anisole compounds;
Partial hydrides of terphenyl derivatives and cycloalkylbenzene derivatives;
Alkylbenzene derivatives having a tertiary hydride directly bonded to a hydride of a terphenyl derivative and a benzene ring;
An alkylbenzene derivative having a quaternary carbon directly bonded to the hydride of the terphenyl derivative and the benzene ring;
A partial hydride of a terphenyl derivative and an aromatic compound having an oxygen atom;
Partially hydrides of terphenyl derivatives and partially fluorinated aromatic compounds;
Partial hydrides of terphenyl derivatives and fluorine-containing anisole compounds;

An alkylbenzene derivative having a tertiary carbon bonded directly to the benzene ring and a cycloalkylbenzene derivative;
An alkylbenzene derivative having a cycloalkylbenzene and a quaternary carbon directly bonded to the benzene ring;
A cycloalkylbenzene derivative and an aromatic compound having an oxygen atom;
Partially fluorinated products of cycloalkylbenzene derivatives and aromatic compounds;
A cycloalkylbenzene derivative and a fluorine-containing anisole compound;

An alkylbenzene derivative having a tertiary carbon directly bonded to the benzene ring and an alkylbenzene derivative having a quaternary carbon directly bonded to the benzene ring;
An alkylbenzene derivative having a tertiary carbon directly bonded to a benzene ring and an aromatic compound having an oxygen atom;
A partially fluorinated product of an aromatic compound and an alkylbenzene derivative having a tertiary carbon directly bonded to the benzene ring;
An alkylbenzene derivative having a tertiary carbon directly bonded to a benzene ring and a fluorine-containing anisole compound;
An alkylbenzene derivative having a quaternary carbon directly bonded to a benzene ring and an aromatic compound having an oxygen atom;
A partially fluorinated product of an aromatic compound and an alkylbenzene derivative having a quaternary carbon directly bonded to the benzene ring;
An alkylbenzene derivative having a quaternary carbon directly bonded to a benzene ring and a fluorine-containing anisole compound;

An aromatic compound having an oxygen atom and a partially fluorinated product of the aromatic compound;
An aromatic compound having an oxygen atom and a fluorine-containing anisole compound;

Partially fluorinated aromatic compounds and fluorinated anisole compounds;
Etc.

Specific examples of these include a combination of biphenyl and o-terphenyl,
A combination of biphenyl and m-terphenyl,
A combination of biphenyl and a partial hydride of a terphenyl derivative,
A combination of biphenyl and cumene,
A combination of biphenyl and cyclopentylbenzene,
A combination of biphenyl and cyclohexylbenzene,
A combination of biphenyl and t-butylbenzene,
A combination of biphenyl and t-amylbenzene,
A combination of biphenyl and diphenyl ether,
A combination of biphenyl and dibenzofuran,
A combination of biphenyl and fluorobenzene,
A combination of biphenyl and benzotrifluoride,
A combination of biphenyl and 2-fluorobiphenyl,
A combination of biphenyl and o-fluorocyclohexylbenzene,
A combination of biphenyl and p-fluorocyclohexylbenzene;
A combination of biphenyl and 2,4-difluoroanisole,

a combination of o-terphenyl and a partial hydride of a terphenyl derivative;
a combination of o-terphenyl and cumene,
a combination of o-terphenyl and cyclopentylbenzene;
a combination of o-terphenyl and cyclohexylbenzene;
a combination of o-terphenyl and t-butylbenzene;
a combination of o-terphenyl and t-amylbenzene;
a combination of o-terphenyl and diphenyl ether;
a combination of o-terphenyl and dibenzofuran,
a combination of o-terphenyl and fluorobenzene,
a combination of o-terphenyl and benzotrifluoride,
a combination of o-terphenyl and 2-fluorobiphenyl;
a combination of o-terphenyl and o-fluorocyclohexylbenzene;
a combination of o-terphenyl and p-fluorocyclohexylbenzene;
a combination of o-terphenyl and 2,4-difluoroanisole,

a combination of m-terphenyl and a partial hydride of a terphenyl derivative;
a combination of m-terphenyl and cumene,
a combination of m-terphenyl and cyclopentylbenzene;
a combination of m-terphenyl and cyclohexylbenzene;
a combination of m-terphenyl and t-butylbenzene;
a combination of m-terphenyl and t-amylbenzene;
a combination of m-terphenyl and diphenyl ether;
a combination of m-terphenyl and dibenzofuran,
a combination of m-terphenyl and fluorobenzene,
a combination of m-terphenyl and benzotrifluoride,
a combination of m-terphenyl and 2-fluorobiphenyl;
a combination of m-terphenyl and o-fluorocyclohexylbenzene;
a combination of m-terphenyl and p-fluorocyclohexylbenzene;
a combination of m-terphenyl and 2,4-difluoroanisole,

A combination of partial hydrides of terphenyl derivatives and cumene,
A combination of a partial hydride of a terphenyl derivative and cyclopentylbenzene,
A combination of a partial hydride of a terphenyl derivative and cyclohexylbenzene,
A combination of a partial hydride of a terphenyl derivative and t-butylbenzene,
A combination of a partial hydride of a terphenyl derivative and t-amylbenzene,
A combination of a partial hydride of a terphenyl derivative and diphenyl ether,
A combination of a partial hydride of a terphenyl derivative and dibenzofuran,
A combination of a partial hydride of a terphenyl derivative and fluorobenzene,
A combination of a partial hydride of a terphenyl derivative and benzotrifluoride,
A combination of a partial hydride of a terphenyl derivative and 2-fluorobiphenyl,
A combination of a partial hydride of a terphenyl derivative and o-fluorocyclohexylbenzene,
A combination of a partial hydride of a terphenyl derivative and p-fluorocyclohexylbenzene,
A combination of a partial hydride of a terphenyl derivative and 2,4-difluoroanisole,

A combination of cumene and cyclopentylbenzene,
A combination of cumene and cyclohexylbenzene,
A combination of cumene and t-butylbenzene,
A combination of cumene and t-amylbenzene,
A combination of cumene and diphenyl ether,
A combination of cumene and dibenzofuran,
A combination of cumene and fluorobenzene,
A combination of cumene and benzotrifluoride,
A combination of cumene and 2-fluorobiphenyl,
A combination of cumene and o-fluorocyclohexylbenzene;
A combination of cumene and p-fluorocyclohexylbenzene;
A combination of cumene and 2,4-difluoroanisole,

A combination of cyclohexylbenzene and t-butylbenzene,
A combination of cyclohexylbenzene and t-amylbenzene;
A combination of cyclohexylbenzene and diphenyl ether,
A combination of cyclohexylbenzene and dibenzofuran,
A combination of cyclohexylbenzene and fluorobenzene,
A combination of cyclohexylbenzene and benzotrifluoride,
A combination of cyclohexylbenzene and 2-fluorobiphenyl,
A combination of cyclohexylbenzene and o-fluorocyclohexylbenzene,
A combination of cyclohexylbenzene and p-fluorocyclohexylbenzene,
A combination of cyclohexylbenzene and 2,4-difluoroanisole,

a combination of t-butylbenzene and t-amylbenzene;
a combination of t-butylbenzene and diphenyl ether;
a combination of t-butylbenzene and dibenzofuran,
a combination of t-butylbenzene and fluorobenzene,
a combination of t-butylbenzene and benzotrifluoride,
a combination of t-butylbenzene and 2-fluorobiphenyl;
a combination of t-butylbenzene and o-fluorocyclohexylbenzene;
a combination of t-butylbenzene and p-fluorocyclohexylbenzene;
a combination of t-butylbenzene and 2,4-difluoroanisole,

a combination of t-amylbenzene and diphenyl ether;
a combination of t-amylbenzene and dibenzofuran;
a combination of t-amylbenzene and fluorobenzene,
a combination of t-amylbenzene and benzotrifluoride,
a combination of t-amylbenzene and 2-fluorobiphenyl;
a combination of t-amylbenzene and o-fluorocyclohexylbenzene;
a combination of t-amylbenzene and p-fluorocyclohexylbenzene;
a combination of t-amylbenzene and 2,4-difluoroanisole,

A combination of diphenyl ether and dibenzofuran,
A combination of diphenyl ether and fluorobenzene,
A combination of diphenyl ether and benzotrifluoride,
A combination of diphenyl ether and 2-fluorobiphenyl,
A combination of diphenyl ether and o-fluorocyclohexylbenzene;
A combination of diphenyl ether and p-fluorocyclohexylbenzene;
A combination of diphenyl ether and 2,4-difluoroanisole,

A combination of dibenzofuran and fluorobenzene,
A combination of dibenzofuran and benzotrifluoride,
A combination of dibenzofuran and 2-fluorobiphenyl,
A combination of dibenzofuran and o-fluorocyclohexylbenzene;
A combination of dibenzofuran and p-fluorocyclohexylbenzene;
A combination of dibenzofuran and 2,4-difluoroanisole,

A combination of fluorobenzene and benzotrifluoride,
A combination of fluorobenzene and 2-fluorobiphenyl,
A combination of fluorobenzene and o-fluorocyclohexylbenzene,
A combination of fluorobenzene and p-fluorocyclohexylbenzene,
A combination of fluorobenzene and 2,4-difluoroanisole,

A combination of benzotrifluoride and 2-fluorobiphenyl,
A combination of benzotrifluoride and o-fluorocyclohexylbenzene;
A combination of benzotrifluoride and p-fluorocyclohexylbenzene;
A combination of benzotrifluoride and 2,4-difluoroanisole,

A combination of 2-fluorobiphenyl and o-fluorocyclohexylbenzene,
A combination of 2-fluorobiphenyl and p-fluorocyclohexylbenzene;
A combination of 2-fluorobiphenyl and 2,4-difluoroanisole,

a combination of o-fluorocyclohexylbenzene and p-fluorocyclohexylbenzene;
a combination of o-fluorocyclohexylbenzene and 2,4-difluoroanisole,
a combination of p-fluorocyclohexylbenzene and 2,4-difluoroanisole,
Etc.

  When the nonaqueous electrolytic solution of the present invention contains an overcharge inhibitor, the concentration thereof is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 0.1% by mass or more with respect to the entire nonaqueous electrolytic solution. It is desirable to set it as the range of 5 mass% or less.

  If the non-aqueous electrolyte of the present invention contains an overcharge inhibitor within a range that does not significantly impair the effects of the present invention, the overcharge protection circuit such as an incorrect usage or an abnormality of the charging device should operate normally. Even if the battery is overcharged due to the situation, it is preferable because the safety of the non-aqueous electrolyte secondary battery is improved.

<1-5-2-2. Auxiliary>
Specific examples of the auxiliary agent for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage include, for example,
Carbonate compounds other than those corresponding to specific carbonates such as erythritan carbonate and spirobisdimethylene carbonate;
Ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, methyl methanesulfonate, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone, methylphenyl sulfone, tetramethylthiuram monosulfide, N, N-dimethylmethane Sulfur-containing compounds such as sulfonamide, N, N-diethylmethanesulfonamide, and the like;
Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide;
Hydrocarbon compounds such as heptane, octane, cycloheptane;
Etc.

[2. Non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery of the present invention comprises the non-aqueous electrolyte of the present invention and a positive electrode and a negative electrode capable of occluding and releasing ions. Moreover, the non-aqueous electrolyte secondary battery of the present invention may have other configurations.

<2-1. Battery configuration>
The non-aqueous electrolyte secondary battery of the present invention is the same as the conventionally known non-aqueous electrolyte secondary battery except for the negative electrode and the non-aqueous electrolyte. Usually, the non-aqueous electrolyte of the present invention is the same as the non-aqueous electrolyte secondary battery. A positive electrode and a negative electrode are laminated via an impregnated porous film (separator), and these are housed in a case (exterior body). Therefore, the shape of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

<2-2. Non-aqueous electrolyte>
As the non-aqueous electrolyte, the above-described non-aqueous electrolyte of the present invention is used. In addition, in the range which does not deviate from the meaning of this invention, it is also possible to mix | blend and use other nonaqueous electrolyte solutions with respect to the nonaqueous electrolyte solution of this invention.

<2-3. Negative electrode>
The negative electrode active material used for the negative electrode is described below.
The negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. Specific examples thereof include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like.

<2-3-1. Carbonaceous material>
As a carbonaceous material used as a negative electrode active material,
(1) natural graphite,
(2) a carbonaceous material obtained by heat-treating an artificial carbonaceous material and an artificial graphite material at least once in the range of 400 to 3200 ° C .;
(3) a carbonaceous material in which the negative electrode active material layer is composed of at least two types of carbonaceous materials having different crystallinity and / or has an interface in contact with the different crystalline carbonaceous materials,
(4) a carbonaceous material in which the negative electrode active material layer is composed of carbonaceous materials having at least two or more different orientations and / or has an interface in contact with the carbonaceous materials having different orientations;
Is preferably a good balance between initial irreversible capacity and high current density charge / discharge characteristics. Moreover, the carbonaceous materials (1) to (4) may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of the artificial carbonaceous material and the artificial graphite material of (2) above include natural graphite, coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, or those obtained by oxidizing these pitches, Needle coke, pitch coke and carbon materials partially graphitized thereof, furnace black, acetylene black, organic pyrolysis products such as pitch-based carbon fibers, carbonizable organic materials, and these carbides or carbonizable organic materials Examples thereof include solutions dissolved in low-molecular organic solvents such as benzene, toluene, xylene, quinoline, and n-hexane, and carbides thereof.

  Specific examples of the above carbonizable organic substances include coal tar pitch from soft pitch to hard pitch, or heavy coal based oil such as dry distillation liquefied oil, normal pressure residual oil, and direct current of reduced pressure residual oil. Heavy oils such as ethylene tar produced as a by-product during pyrolysis of heavy oils such as heavy oil, crude oil, naphtha, etc., and aromatic hydrocarbons such as acenaphthylene, decacyclene, anthracene, phenanthrene, and nitrogen atom-containing complexes such as phenazine and acridine Cyclic compounds, sulfur-containing heterocyclic compounds such as thiophene and bithiophene, polyphenylenes such as biphenyl and terphenyl, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, insolubilized products of these, nitrogen-containing polyacrylonitrile , Organic polymers such as polypyrrole, sulfur-containing polythiophene, polystyrene, etc. Organic polymers, cellulose, lignin, mannan, polygalacturonic acid, chitosan, natural polymers such as polysaccharides represented by sucrose, thermoplastic resins such as polyphenylene sulfide and polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin And thermosetting resins such as imide resins.

<2-3-2. Configuration, physical properties, preparation method of carbonaceous negative electrode>
Regarding the properties of the carbonaceous material, the negative electrode containing the carbonaceous material, the electrodeification method, the current collector, and the nonaqueous electrolyte secondary battery, any one of (1) to (18) shown below or It is desirable to satisfy multiple terms simultaneously.

(1) X-ray parameters The d-value (interlayer distance) of the lattice plane (002 plane) obtained by X-ray diffraction by the Gakushin method of carbonaceous materials is usually 0.335 to 0.340 nm, particularly 0.335. Those having a thickness of ˜0.338 nm, particularly 0.335 to 0.337 nm are preferred. The crystallite size (Lc) determined by X-ray diffraction by the Gakushin method is usually 1.0 nm or more, preferably 1.5 nm or more, and particularly preferably 2 nm or more.

  The graphite surface coated with amorphous carbon is preferably graphite having a d-value of 0.335 to 0.338 nm on the lattice plane (002 plane) in X-ray diffraction as a core material. A carbonaceous material having a larger d-value on the lattice plane (002 plane) in X-ray diffraction than the core material is attached, and the d-value on the lattice plane (002 plane) in X-ray diffraction is greater than that of the core material and the core material. The ratio with respect to the carbonaceous material having a large is 99/1 to 80/20 by weight. When this is used, a negative electrode having a high capacity and hardly reacting with the electrolytic solution can be produced.

(2) Ash content The ash content in the carbonaceous material is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, based on the total mass of the carbonaceous material. It is preferably 1 ppm or more. When the weight ratio of ash exceeds the above range, deterioration of battery performance due to reaction with the non-aqueous electrolyte during charge / discharge may not be negligible. On the other hand, if it falls below the above range, the production requires a lot of time, energy and equipment for preventing contamination, which may increase the cost.

(3) Volume-based average particle size The volume-based average particle size of the carbonaceous material is usually a volume-based average particle size (median diameter) determined by a laser diffraction / scattering method of 1 μm or more, preferably 3 μm or more, It is more preferably 5 μm or more, particularly preferably 7 μm or more, and usually 100 μm or less, preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 25 μm or less. If the volume-based average particle size is below the above range, the irreversible capacity may increase, leading to loss of initial battery capacity. On the other hand, when the above range is exceeded, when an electrode is produced by coating, an uneven coating surface tends to be formed, which may be undesirable in the battery production process.

  The volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and laser diffraction / scattering particle size distribution. This is carried out using a meter (LA-700 manufactured by Horiba, Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material of the present invention.

(4) Raman R value, Raman half-value width As for the Raman R value of the carbonaceous material, a value measured by using an argon ion laser Raman spectrum method is usually 0.01 or more, preferably 0.03 or more, preferably 1 or more is more preferable, and it is usually 1.5 or less, preferably 1.2 or less, more preferably 1 or less, and particularly preferably 0.5 or less.

  When the Raman R value is below the above range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge / discharge. That is, charge acceptance may be reduced. In addition, when the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics. On the other hand, if it exceeds the above range, the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.

Further, the Raman half-width in the vicinity of 1580 cm ^{−1 of the} carbonaceous material is not particularly limited, but is usually 10 cm ⁻¹ or more, preferably 15 cm ⁻¹ or more, and usually 100 cm ⁻¹ or less, and 80 cm ⁻¹ or less. Preferably, 60 cm ⁻¹ or less is more preferable, and 40 cm ⁻¹ or less is particularly preferable. If the Raman half width is less than the above range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge and discharge. That is, charge acceptance may be reduced. In addition, when the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics. On the other hand, if it exceeds the above range, the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.

The measurement of the Raman spectrum, using a Raman spectrometer (manufactured by JASCO Corporation Raman spectrometer), the sample is naturally dropped into the measurement cell and filled, and while irradiating the sample surface in the cell with argon ion laser light, This is done by rotating the cell in a plane perpendicular to the laser beam. The resulting Raman spectrum, the intensity _{I A} of the peak _{P A} in the vicinity of 1580 cm ^-1, and measuring the intensity _{I B} of a peak _{P B} in the vicinity of 1360 cm ^-1, the intensity ratio _{R (R = I B / I} A) Is calculated. The Raman R value calculated by the measurement is defined as the Raman R value of the carbonaceous material in the present invention. Further, the half width of the peak P _A in the vicinity of 1580 cm ^-1 of the resulting Raman spectrum was measured, which is defined as the Raman half-value width of the carbonaceous material in the present invention.

Moreover, said Raman measurement conditions are as follows.
Argon ion laser wavelength: 514.5nm
・ Laser power on the sample: 15-25mW
・ Resolution: 10-20cm ^-1
Measurement range: 1100 cm ^{−1 to} 1730 cm ⁻¹
・ Raman R value, Raman half width analysis: Background processing ・ Smoothing processing: Simple average, 5 points of convolution

(5) BET specific surface area As for the BET specific surface area of the carbonaceous material, the value of the specific surface area measured using the BET method is usually 0.1 m ² · g ⁻¹ or more, and 0.7 m ² · g ⁻¹ or more. Is preferably 1.0 m ² · g ⁻¹ or more, more preferably 1.5 m ² · g ⁻¹ or more, and usually 100 m ² · g ⁻¹ or less, and 25 m ² · g ⁻¹ or less. It is preferably 15 m ² · g ⁻¹ or less, more preferably 10 m ² · g ⁻¹ or less. When the value of the BET specific surface area is less than this range, the acceptability of lithium is likely to deteriorate during charging when used as a negative electrode material, lithium is likely to precipitate on the electrode surface, and stability may be reduced. On the other hand, if it exceeds this range, when used as a negative electrode material, the reactivity with the non-aqueous electrolyte increases, gas generation tends to increase, and a preferable battery may be difficult to obtain.

  The specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately adjusted so that the value of the relative pressure becomes 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used. The specific surface area determined by the measurement is defined as the BET specific surface area of the carbonaceous material in the present invention.

(6) Pore size distribution The pore size distribution of the carbonaceous material is calculated by measuring the mercury intrusion amount. By using mercury porosimetry (mercury intrusion method), fine pores with a diameter of 0.01 μm or more and 1 μm or less with voids in particles of carbonaceous material, irregularities due to steps on the particle surface, and contact surfaces between particles, etc. carbonaceous material to be measured to correspond to the holes, usually 0.01 cm ³ · ^{g -1} or more, preferably 0.05 cm ³ · ^{g -1} or more, more preferably 0.1 cm ³ · ^{g -1} or more, It is usually desirable to have a pore size distribution of 0.6 cm ³ · g ⁻¹ or less, preferably 0.4 cm ³ · g ⁻¹ or less, more preferably 0.3 cm ³ · g ⁻¹ or less. If the pore size distribution exceeds the above range, a large amount of binder may be required when forming an electrode plate. On the other hand, if it falls below the above range, the high current density charge / discharge characteristics may be deteriorated, and the effect of relaxing the expansion and contraction of the electrode during charge / discharge may not be obtained.

Further, the total pore volume, which is obtained by mercury porosimetry (mercury intrusion method) and corresponds to pores having a diameter of 0.01 μm or more and 100 μm or less, is usually 0.1 cm ³ · g ⁻¹ or more, and 25 cm ³ · ^{g -1} or more, more preferably 0.4 cm ³ · ^{g -1} or higher, and is generally 10 cm ³ · ^{g -1} or less, preferably ^{5 cm} 3 · ^{g -1} or less, ^{2 cm} 3 · g ^-1 or less is more preferable. If the total pore volume exceeds the above range, a large amount of binder may be required when forming an electrode plate. On the other hand, if the amount is below the above range, the effect of dispersing the thickener or the binder may not be obtained when forming the electrode plate.

  The average pore diameter is usually 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more, and usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less. If the average pore diameter exceeds the above range, a large amount of binder may be required. Moreover, when it is less than the above range, the high current density charge / discharge characteristics may deteriorate.

  The mercury intrusion is measured using a mercury porosimeter (Autopore 9520: manufactured by Micromeritex Corporation) as an apparatus for mercury porosimetry. As a pretreatment, about 0.2 g of a sample is sealed in a powder cell and deaerated for 10 minutes at room temperature under vacuum (50 μmHg or less). Subsequently, the pressure is reduced to 4 psia (about 28 kPa), mercury is introduced, the pressure is increased stepwise from 4 psia (about 28 kPa) to 40000 psia (about 280 MPa), and then the pressure is reduced to 25 psia (about 170 kPa). The number of steps at the time of pressure increase is 80 points or more, and the mercury intrusion amount is measured after an equilibration time of 10 seconds in each step.

From the mercury intrusion curve thus obtained, the pore size distribution is calculated using the Washburn equation. Note that the surface tension (γ) of mercury is 485 dyne · cm ⁻¹ ( ¹ dyne = 10 μN), and the contact angle (ψ) is 140 °. As the average pore diameter, the pore diameter when the cumulative pore volume is 50% is used.

(7) Circularity When the circularity is measured as a spherical degree of the carbonaceous material, it is preferably within the following range. The circularity is defined as “circularity = (peripheral length of an equivalent circle having the same area as the particle projection shape) / (actual perimeter of the particle projection shape)”, and is theoretical when the circularity is 1. Become a true sphere.

  The circularity of the particles having a particle size of 3 to 40 μm in the range of the carbonaceous material is desirably closer to 1, and is preferably 0.1 or more, more preferably 0.5 or more, and more preferably 0.8 or more, 0.85 or more is more preferable, and 0.9 or more is particularly preferable.

  High current density charge / discharge characteristics improve as the degree of circularity increases. Therefore, when the circularity is less than the above range, the filling property of the negative electrode active material is lowered, the resistance between particles is increased, and the high current density charge / discharge characteristics may be lowered for a short time.

  The circularity is measured using a flow type particle image analyzer (FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute. The detection range is specified as 0.6 to 400 μm, and the particle size is measured in the range of 3 to 40 μm. The circularity obtained by the measurement is defined as the circularity of the carbonaceous material in the present invention.

  The method for improving the degree of circularity is not particularly limited, but a spheroidized sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable. Examples of spheroidizing treatment include a method of mechanically approximating a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by an adhesive force possessed by a binder or particles, etc. Is mentioned.

True density of (8) True Density carbonaceous material is usually 1.4 g · ^{cm -3} or higher, preferably 1.6 g · ^{cm -3} or more, more preferably 1.8 g · ^{cm -3} or more, 2. 0 g · ^{cm -3} or more are particularly preferred, also, usually less than 2.26 g · ^{cm -3.} When the true density is below the above range, the crystallinity of carbon is too low, and the initial irreversible capacity may increase. The upper limit of the above range is the theoretical upper limit of the true density of graphite.

  The true density of the carbonaceous material is measured by a liquid phase substitution method (pycnometer method) using butanol. The value obtained by the measurement is defined as the true density of the carbonaceous material in the present invention.

(9) Tap density The tap density of the carbonaceous material is usually 0.1 g · cm ⁻³ or more, preferably 0.5 g · cm ⁻³ or more, more preferably 0.7 g · cm ⁻³ or more, and 1 g · cm ⁻³ or more is particularly preferable, 2 g · cm ⁻³ or less is preferable, 1.8 g · cm ⁻³ or less is more preferable, and 1.6 g · cm ⁻³ or less is particularly preferable. When the tap density is below the above range, the packing density is difficult to increase when used as a negative electrode, and a high-capacity battery may not be obtained. On the other hand, when the above range is exceeded, there are too few voids between particles in the electrode, it is difficult to ensure conductivity between the particles, and it may be difficult to obtain preferable battery characteristics.

The tap density is measured by passing through a sieve having an opening of 300 μm, dropping the sample onto a 20 cm ³ tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the tap density is calculated from the volume at that time and the weight of the sample. The tap density calculated by the measurement is defined as the tap density of the carbonaceous material in the present invention.

(10) Orientation ratio The orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less. When the orientation ratio is below the above range, the high-density charge / discharge characteristics may deteriorate. The upper limit of the above range is the theoretical upper limit value of the orientation ratio of the carbonaceous material.

The orientation ratio is measured by X-ray diffraction after pressure-molding the sample. Fill the molding machine obtained by filling 0.47g of the sample into a molding machine with a diameter of 17mm and compressing it with 58.8MN · m ^{-2 so} that it is flush with the surface of the sample holder for measurement. X-ray diffraction is measured. From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon, a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated. The orientation ratio calculated by the measurement is defined as the orientation ratio of the carbonaceous material in the present invention.

The X-ray diffraction measurement conditions are as follows. “2θ” indicates a diffraction angle.
・ Target: Cu (Kα ray) graphite monochromator ・ Slit:
Divergence slit = 0.5 degree Light receiving slit = 0.15 mm
Scattering slit = 0.5 degree / measurement range and step angle / measurement time:
(110) plane: 75 degrees ≦ 2θ ≦ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ≦ 2θ ≦ 57 degrees 1 degree / 60 seconds

(11) Aspect ratio (powder)
The aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. If the aspect ratio exceeds the above range, streaking or a uniform coated surface cannot be obtained when forming an electrode plate, and the high current density charge / discharge characteristics may deteriorate. The lower limit of the above range is the theoretical lower limit value of the aspect ratio of the carbonaceous material.

  The aspect ratio is measured by magnifying and observing the carbonaceous material particles with a scanning electron microscope. Carbonaceous material when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 microns or less and rotating and tilting the stage on which the sample is fixed. The longest diameter A of the particles and the shortest diameter B orthogonal to the same are measured, and the average value of A / B is obtained. The aspect ratio (A / B) obtained by the measurement is defined as the aspect ratio of the carbonaceous material in the present invention.

(12) Secondary material mixing The secondary material mixing means that two or more carbonaceous materials having different properties are contained in the negative electrode and / or the negative electrode active material. The properties referred to here are selected from the group consisting of X-ray diffraction parameters, median diameter, aspect ratio, BET specific surface area, orientation ratio, Raman R value, tap density, true density, pore distribution, circularity, and ash content. Shows more than one characteristic.

  As a particularly preferred example of mixing these secondary materials, the volume-based particle size distribution is not symmetrical when centered on the median diameter, containing two or more carbonaceous materials having different Raman R values, And X-ray parameters are different.

  As an example of the effect of the auxiliary material mixing, carbonaceous materials such as graphite (natural graphite, artificial graphite and the like), carbon black such as acetylene black, and amorphous carbon such as needle coke are contained as a conductive material. Reducing electrical resistance.

  When mixing a conductive material as a secondary material mixture, one type may be mixed alone, or two or more types may be mixed in any combination and ratio. The mixing ratio of the conductive material to the carbonaceous material is usually 0.1% by mass or more and 0.5% by mass or more, more preferably 0.6% by mass or more, and usually 45% by mass or less. Yes, 40 mass% or less is preferable. If the mixing ratio is less than the above range, it may be difficult to obtain the effect of improving conductivity. On the other hand, exceeding the above range may increase the initial irreversible capacity.

(13) Electrode production Any known method can be used for producing an electrode as long as the effects of the present invention are not significantly limited. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.

  The thickness of the negative electrode active material layer per side in the stage immediately before the non-aqueous electrolyte injection process of the battery is usually 15 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and usually 150 μm or less. 120 μm or less is preferable, and 100 μm or less is more preferable. This is because if the thickness of the negative electrode active material exceeds this range, the non-aqueous electrolyte solution hardly penetrates to the vicinity of the current collector interface, and thus the high current density charge / discharge characteristics may be deteriorated. Further, if the ratio is below this range, the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease. Further, the negative electrode active material may be roll-formed to form a sheet electrode, or may be formed into a pellet electrode by compression molding.

(14) Current collector As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable from the viewpoint of ease of processing and cost.

  In addition, the shape of the current collector may be, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, or the like when the current collector is a metal material. Among them, a metal thin film is preferable, and a copper foil is more preferable, and a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method are more preferable, and both can be used as a current collector.

  In addition, when the thickness of the copper foil is less than 25 μm, a copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) having higher strength than pure copper can be used.

  A current collector made of a copper foil produced by a rolling method is suitable for use in a small cylindrical battery because the copper crystals are arranged in the rolling direction so that the negative electrode is hard to crack even if it is rounded sharply or rounded at an acute angle. be able to.

  For example, an electrolytic copper foil is prepared by immersing a metal drum in an electrolytic solution in which copper ions are dissolved, and flowing current while rotating the copper drum, thereby depositing copper on the surface of the drum and peeling it off. It is obtained. Copper may be deposited on the surface of the rolled copper foil by an electrolytic method. One side or both sides of the copper foil may be subjected to a roughening treatment or a surface treatment (for example, a chromate treatment having a thickness of about several nm to 1 μm, a base treatment such as Ti).

  The following physical properties are desired for the current collector substrate.

(14-1) Average surface roughness (Ra)
The average surface roughness (Ra) of the negative electrode active material thin film forming surface of the current collector substrate defined by the method described in JIS B0601-1994 is not particularly limited, but is usually 0.05 μm or more and 0.1 μm or more. Preferably, it is more preferably 0.15 μm or more, and is usually 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.0 μm or less. This is because when the average surface roughness (Ra) of the current collector substrate is within the above range, good charge / discharge cycle characteristics can be expected. Further, the area of the interface with the negative electrode active material thin film is increased, and the adhesion with the negative electrode active material thin film is improved. The upper limit value of the average surface roughness (Ra) is not particularly limited, but those having an average surface roughness (Ra) exceeding 1.5 μm are generally available as foils having a practical thickness as a battery. Since it is difficult, those of 1.5 μm or less are usually used.

(14-2) Tensile strength The tensile strength is obtained by dividing the maximum tensile force required until the test piece breaks by the cross-sectional area of the test piece. The tensile strength in the present invention is measured by the same apparatus and method as described in JISZ2241 (metal material tensile test method).

The tensile strength of the current collector substrate is not particularly limited, is usually 100 N · ^{mm -2} or more, preferably 250 N · ^{mm -2} or more, more preferably 400 N · ^{mm -2} or more, 500 N · ^{mm -2} or more Particularly preferred. The tensile strength is preferably as high as possible, but is usually 1000 N · mm ⁻² or less from the viewpoint of industrial availability. If the current collector substrate has a high tensile strength, cracking of the current collector substrate due to expansion / contraction of the negative electrode active material thin film accompanying charging / discharging can be suppressed, and good cycle characteristics can be obtained.

(14-3) 0.2% proof stress 0.2% proof stress is the magnitude of a load required to give a plastic (permanent) strain of 0.2%. It means that 0.2% deformation has occurred even when loaded. The 0.2% yield strength is measured with the same equipment and method as the tensile strength.

0.2% proof stress of the current collector substrate is not particularly limited, normally 30 N · ^{mm -2} or more, preferably 150 N · ^{mm -2} or more, particularly preferably 300N · ^{mm -2} or more. The 0.2% resistance value is preferably as high as possible, but 900 N · mm ⁻² or less is usually desirable from the viewpoint of industrial availability. If the current collector substrate has a high 0.2% proof stress, plastic deformation of the current collector substrate due to expansion / contraction of the negative electrode active material thin film accompanying charging / discharging can be suppressed, and good cycle characteristics can be obtained. Can do.

(14-4) Thickness of current collector Although the thickness of the current collector is arbitrary, it is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and usually 1 mm or less, 100 μm or less. Is preferable, and 30 μm or less is more preferable. When the thickness of the current collector is thinner than 1 μm, the strength may be reduced, which may make application difficult. Moreover, when it becomes thicker than 100 micrometers, the shape of electrodes, such as winding, may be changed. The current collector may be mesh.

(15) Ratio of thickness of current collector and negative electrode active material layer The ratio of the thickness of current collector and negative electrode active material layer is not particularly limited. The value of “material layer thickness) / (current collector thickness)” is preferably 150 or less, more preferably 20 or less, particularly preferably 10 or less, more preferably 0.1 or more, and 0.4 or more. More preferred is 1 or more.

  When the ratio of the thickness of the current collector to the negative electrode active material layer exceeds the above range, the current collector may generate heat due to Joule heat during high current density charge / discharge. On the other hand, below the above range, the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease.

(16) Electrode density The electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g · cm ⁻³ or more. 2 g · cm ⁻³ or more is more preferable, 1.3 g · cm ⁻³ or more is particularly preferable, 2 g · cm ⁻³ or less is preferable, 1.9 g · cm ⁻³ or less is more preferable, and 1.8 g · cm. ⁻³ or less is more preferable, and 1.7 g · cm ⁻³ or less is particularly preferable. When the density of the negative electrode active material existing on the current collector exceeds the above range, the negative electrode active material particles are destroyed, and the initial irreversible capacity increases or non-aqueous system near the current collector / negative electrode active material interface. There is a case where high current density charge / discharge characteristics are deteriorated due to a decrease in permeability of the electrolytic solution. On the other hand, if the amount is less than the above range, the conductivity between the negative electrode active materials decreases, the battery resistance increases, and the capacity per unit volume may decrease.

(17) Binder The binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte and the solvent used during electrode production.

  Specific examples include resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, NBR ( Acrylonitrile / butadiene rubber), rubbery polymers such as ethylene / propylene rubber; styrene / butadiene / styrene block copolymers or hydrogenated products thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Thermoplastic elastomeric polymer such as butadiene / styrene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated product thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene Soft resinous polymers such as vinyl acetate copolymer and propylene / α-olefin copolymer; Fluorine-based polymers such as polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene / ethylene copolymer Polymers: Polymer compositions having ionic conductivity of alkali metal ions (particularly lithium ions), and the like. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  The solvent for forming the slurry is not particularly limited as long as it is a solvent capable of dissolving or dispersing the negative electrode active material, the binder, and the thickener and conductive material used as necessary. Alternatively, either an aqueous solvent or an organic solvent may be used.

  Examples of the aqueous solvent include water, alcohol and the like, and examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N , N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane and the like.

  In particular, when an aqueous solvent is used, it is preferable to add a dispersant or the like in addition to the thickener and slurry it using a latex such as SBR. In addition, these solvents may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less, 15% by mass. The following is more preferable, 10 mass% or less is still more preferable, and 8 mass% or less is especially preferable. When the ratio of the binder with respect to a negative electrode active material exceeds the said range, the binder ratio from which the amount of binders does not contribute to battery capacity may increase, and the fall of battery capacity may be caused. On the other hand, below the above range, the strength of the negative electrode may be reduced.

  In particular, when a rubbery polymer typified by SBR is contained as a main component, the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, and 0 .6% by mass or more is more preferable, and is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.

  Moreover, when the main component contains a fluorine-based polymer typified by polyvinylidene fluoride, the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. Preferably, it is usually 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.

  A thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  Furthermore, when using a thickener, the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Moreover, it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is still more preferable. When the ratio of the thickener to the negative electrode active material is less than the above range, applicability may be significantly reduced. Moreover, when it exceeds the said range, the ratio of the negative electrode active material which occupies for a negative electrode active material layer will fall, and the problem that the capacity | capacitance of a battery falls and the resistance between negative electrode active materials may increase.

(18) Electrode orientation ratio The electrode orientation ratio is usually 0.001 or more, preferably 0.005 or more, more preferably 0.01 or more, and usually 0.67 or less. When the electrode plate orientation ratio is below the above range, the high-density charge / discharge characteristics may be deteriorated. The upper limit of the above range is the theoretical upper limit of the electrode plate orientation ratio of the carbonaceous material.

  The electrode plate orientation ratio is measured by measuring the orientation ratio of the negative electrode active material of the electrode by X-ray diffraction for the negative electrode after being pressed to the target density. Although a specific method is not particularly limited, as a standard method, peak separation is performed by fitting peaks of carbon (110) diffraction and (004) diffraction by X-ray diffraction using asymmetric Pearson VII as a profile function. To calculate the integrated intensities of the peaks of (110) diffraction and (004) diffraction, respectively. From the obtained integrated intensity, a ratio represented by (110) diffraction integrated intensity / (004) diffraction integrated intensity is calculated. The electrode negative electrode active material orientation ratio calculated by this measurement is defined as the electrode plate orientation ratio of the carbonaceous material in the present invention.

The X-ray diffraction measurement conditions are as follows. “2θ” indicates a diffraction angle.
-Target: Cu (Kα ray) graphite monochromator-Slit: Divergence slit = 1 degree, Receiving slit = 0.1 mm, Scattering slit = 1 degree-Measurement range and step angle / measurement time:
(110) plane: 76.5 degrees ≦ 2θ ≦ 78.5 degrees 0.01 degrees / 3 seconds (004) plane: 53.5 degrees ≦ 2θ ≦ 56.0 degrees 0.01 degrees / 3 seconds Sample preparation: Fix the electrode to the glass plate with double-sided tape with a thickness of 0.1 mm

<2-3-3. Structure, physical properties, and preparation method of negative electrode using metal compound material and metal compound material>
As the metal compound-based material used as the negative electrode active material, if lithium can be occluded / released, a single metal or alloy that forms a lithium alloy, or an oxide, carbide, nitride, silicide, sulfide, Any compound such as phosphide is not particularly limited. Examples of such metal compounds include compounds containing metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, and Zn. Among these, a single metal or an alloy that forms a lithium alloy is preferable, and a material containing a group 13 or group 14 metal / metalloid element (that is, excluding carbon) is more preferable. Further, silicon (Si ), Tin (Sn) or lead (Pb) (hereinafter, these three elements may be referred to as “specific metal elements”), simple metals, alloys containing these atoms, or their metals (specific metal elements) It is preferable that it is a compound of these. These may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the negative electrode active material having at least one kind of atom selected from the specific metal element include a single metal of any one specific metal element, an alloy composed of two or more specific metal elements, one type, or two or more types Alloys composed of the specified metal element and one or more other metal elements, and compounds containing one or more specified metal elements, or oxides, carbides and nitrides of the compounds -Complex compounds such as silicides, sulfides and phosphides are listed. By using these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.

  Moreover, the compound which these complex compounds combined with several elements, such as a metal simple substance, an alloy, or a nonmetallic element, can also be mentioned as an example. More specifically, for example, in silicon and tin, an alloy of these elements and a metal that does not operate as a negative electrode can be used. For example, in the case of tin, a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not operate as a negative electrode, and a nonmetallic element can also be used. .

  Among these negative electrode active materials, since the capacity per unit weight is large when a battery is formed, any one metal element of a specific metal element, an alloy of two or more specific metal elements, oxidation of a specific metal element In particular, silicon and / or tin metal simple substance, alloy, oxide, carbide, nitride and the like are preferable from the viewpoint of capacity per unit weight and environmental load.

In addition, the following compounds containing silicon and / or tin are also preferable because the cycle characteristics are excellent, although the capacity per unit mass is inferior to the use of a single metal or an alloy.
The elemental ratio between silicon and / or tin and oxygen is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, and usually 1.5 or less, preferably 1 .3 or less, more preferably 1.1 or less of silicon and / or tin oxide.
The elemental ratio between silicon and / or tin and nitrogen is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, and usually 1.5 or less, preferably 1 . 3 or less, more preferably 1.1 or less silicon and / or tin nitride.
The elemental ratio of silicon and / or tin to carbon is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, and usually 1.5 or less, preferably 1 .3 or less, more preferably 1.1 or less silicon and / or tin carbide.

  In addition, any one of the above-described negative electrode active materials may be used alone, or two or more thereof may be used in any combination and ratio.

  The negative electrode in the non-aqueous electrolyte secondary battery of the present invention can be manufactured using any known method. Specifically, as a manufacturing method of the negative electrode, for example, a method in which a negative electrode active material added with a binder or a conductive material is roll-formed as it is to form a sheet electrode, or a compression-molded pellet electrode and The above negative electrode is usually applied to a negative electrode current collector (hereinafter also referred to as “negative electrode current collector”) by a method such as a coating method, a vapor deposition method, a sputtering method, or a plating method. A method of forming a thin film layer (negative electrode active material layer) containing an active material is used. In this case, by adding a binder, a thickener, a conductive material, a solvent, etc. to the above-mentioned negative electrode active material to form a slurry, applying this to the negative electrode current collector, drying, and pressing to increase the density A negative electrode active material layer is formed on the negative electrode current collector.

  Examples of the material of the negative electrode current collector include steel, copper alloy, nickel, nickel alloy, and stainless steel. Of these, copper foil is preferred from the viewpoint of easy processing into a thin film and cost.

  The thickness of the negative electrode current collector is usually 1 μm or more, preferably 5 μm or more, and is usually 100 μm or less, preferably 50 μm or less. This is because if the thickness of the negative electrode current collector is too thick, the capacity of the entire battery may be too low, and conversely if it is too thin, handling may be difficult.

  In addition, in order to improve the binding effect with the negative electrode active material layer formed on the surface, the surface of these negative electrode current collectors is preferably subjected to a roughening treatment in advance. Surface roughening methods include blasting, rolling with a rough surface roll, polishing cloth with a fixed abrasive particle, grinding wheel, emery buff, machine that polishes the current collector surface with a wire brush equipped with steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.

  Further, in order to reduce the weight of the negative electrode current collector and improve the energy density per weight of the battery, a perforated negative electrode current collector such as an expanded metal or a punching metal can be used. This type of negative electrode current collector can be freely changed in weight by changing its aperture ratio. Further, when a negative electrode active material layer is formed on both surfaces of this type of negative electrode current collector, the negative electrode active material layer is further less likely to peel due to the rivet effect through the hole. However, when the aperture ratio becomes too high, the contact area between the negative electrode active material layer and the negative electrode current collector becomes small, and thus the adhesive strength may be lowered.

  The slurry for forming the negative electrode active material layer is usually prepared by adding a binder, a thickener and the like to the negative electrode material. In addition, the “negative electrode material” in this specification refers to a material in which a negative electrode active material and a conductive material are combined.

  The content of the negative electrode active material in the negative electrode material is usually 70% by mass or more, particularly 75% by mass or more, and usually 97% by mass or less, and particularly preferably 95% by mass or less. When the content of the negative electrode active material is too small, the capacity of the secondary battery using the obtained negative electrode tends to be insufficient, and when the content is too large, the content of the binder or the like is relatively insufficient. This is because the strength of the negative electrode tends to be insufficient. When two or more negative electrode active materials are used in combination, the total amount of the negative electrode active materials may be set to satisfy the above range.

  Examples of the conductive material used for the negative electrode include metal materials such as copper and nickel; carbon materials such as graphite and carbon black. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a carbon material as the conductive material because the carbon material acts as an active material. It is preferable that the content of the conductive material in the negative electrode material is usually 3% by mass or more, particularly 5% by mass or more, and usually 30% by mass or less, particularly 25% by mass or less. When the content of the conductive material is too small, the conductivity tends to be insufficient. When the content is too large, the content of the negative electrode active material or the like is relatively insufficient, which tends to decrease the battery capacity and strength. . Note that when two or more conductive materials are used in combination, the total amount of the conductive materials may satisfy the above range.

  As the binder used for the negative electrode, any material can be used as long as it is a material safe with respect to the solvent and the electrolytic solution used at the time of producing the electrode. Examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, styrene / butadiene rubber / isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The content of the binder is usually 0.5 parts by weight or more, particularly 1 part by weight or more, and usually 10 parts by weight or less, particularly 8 parts by weight or less, with respect to 100 parts by weight of the negative electrode material. When the content of the binder is too small, the strength of the obtained negative electrode tends to be insufficient. When the content is too large, the content of the negative electrode active material and the like is relatively insufficient, and thus the battery capacity and conductivity tend to be insufficient. It is because it becomes. In addition, when using two or more binders together, what is necessary is just to make it the total amount of a binder satisfy | fill the said range.

  Examples of the thickener used for the negative electrode include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The thickener may be used as necessary, but when used, the thickener content in the negative electrode active material layer is usually in the range of 0.5 mass% or more and 5 mass% or less. Is preferred.

  The slurry for forming the negative electrode active material layer is prepared by mixing the negative electrode active material with a conductive material, a binder, or a thickener as necessary, and using an aqueous solvent or an organic solvent as a dispersion medium. . As the aqueous solvent, water is usually used, but a solvent other than water such as alcohols such as ethanol and cyclic amides such as N-methylpyrrolidone is used in combination at a ratio of about 30% by mass or less with respect to water. You can also As the organic solvent, usually, cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic carbonization such as anisole, toluene and xylene Examples thereof include alcohols such as hydrogens, butanol and cyclohexanol, among which cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide are preferable. . Any one of these may be used alone, or two or more may be used in any combination and ratio.

  The viscosity of the slurry is not particularly limited as long as it is a viscosity that can be applied onto the current collector. What is necessary is just to adjust suitably by changing the usage-amount of a solvent etc. at the time of preparation of a slurry so that it may become the viscosity which can be apply | coated.

  The obtained slurry is applied onto the above-described negative electrode current collector, dried, and then pressed to form a negative electrode active material layer. The method of application is not particularly limited, and a method known per se can be used. The drying method is not particularly limited, and a known method such as natural drying, heat drying, or reduced pressure drying can be used.

The electrode structure when the negative electrode active material is made into an electrode by the above method is not particularly limited, but the density of the active material present on the current collector is preferably 1 g · cm ⁻³ or more, and 1.2 g · cm ⁻³ or more is more preferable, 1.3 g · cm ⁻³ or more is particularly preferable, 4 g · cm ⁻³ or less is preferable, 3 g · cm ⁻³ or less is more preferable, and 2 g · cm ⁻³ or less is more preferable. When the density of the active material existing on the current collector exceeds the above range, the active material particles are destroyed, the initial irreversible capacity increases, and the non-aqueous electrolyte solution near the current collector / active material interface There is a case where high current density charge / discharge characteristics are deteriorated due to decrease in permeability. On the other hand, below the above range, the conductivity between the active materials may be reduced, the battery resistance may be increased, and the capacity per unit volume may be reduced.

<2-3-4. Lithium-containing metal composite oxide material, and negative electrode configuration, physical properties, and preparation method using lithium-containing metal composite oxide material>
The lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium, but preferably a lithium-containing composite metal oxide material containing titanium, A composite oxide of titanium (hereinafter abbreviated as “lithium titanium composite oxide”) is preferable. That is, it is particularly preferable to use a lithium titanium composite oxide having a spinel structure in a negative electrode active material for a non-aqueous electrolyte secondary battery because the output resistance is greatly reduced.

  In addition, lithium or titanium of the lithium titanium composite oxide is at least selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. Those substituted with one element are also preferred.

  The metal oxide is a lithium titanium composite oxide represented by the general formula (5). In the general formula (5), 0.7 ≦ x ≦ 1.5, 1.5 ≦ y ≦ 2.3, It is preferable that 0 ≦ z ≦ 1.6 because the structure upon doping and dedoping of lithium ions is stable.

_{Li x Ti y M z O 4} (5)
[In General Formula (5), M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. ]

Among the compositions represented by the general formula (5),
(A) 1.2 ≦ x ≦ 1.4, 1.5 ≦ y ≦ 1.7, z = 0
(B) 0.9 ≦ x ≦ 1.1, 1.9 ≦ y ≦ 2.1, z = 0
(C) 0.7 ≦ x ≦ 0.9, 2.1 ≦ y ≦ 2.3, z = 0
This structure is particularly preferable because of a good balance of battery performance.

Particularly preferred representative compositions of the above compounds are Li _4/3 Ti _5/3 O ₄ in (a), Li ₁ Ti ₂ O ₄ in (b), and Li _4/5 Ti _11/5 O in (c). ₄ . As for the structure of Z ≠ 0, for example, Li _4/3 Ti _4/3 Al _1/3 O ₄ is preferable.

  In addition to the above requirements, the lithium titanium composite oxide as the negative electrode active material in the present invention further satisfies at least one of the characteristics such as physical properties and shapes shown in the following (1) to (13). It is preferable to satisfy two or more at the same time.

(1) BET specific surface area As for the BET specific surface area of the lithium titanium composite oxide used as the negative electrode active material, the specific surface area value measured using the BET method is preferably 0.5 m ² · g ⁻¹ or more. 7 m ² · g ⁻¹ or more is more preferred, 1.0 m ² · g ⁻¹ or more is more preferred, 1.5 m ² · g ⁻¹ or more is particularly preferred, and 200 m ² · g ⁻¹ or less is preferred, 100 m ² · g ⁻¹ or less is more preferred, 50 m ² · g ⁻¹ or less is more preferred, and 25 m ² · g ⁻¹ or less is particularly preferred. When the BET specific surface area is less than the above range, the reaction area in contact with the non-aqueous electrolyte when used as the negative electrode material may decrease, and the output resistance may increase. On the other hand, if it exceeds the above range, the surface of the metal oxide crystal containing titanium and the portion of the end face increase, and due to this, crystal distortion also occurs, irreversible capacity cannot be ignored, which is preferable It may be difficult to obtain a battery.

  The specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately adjusted so that the value of the relative pressure becomes 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used. The specific surface area determined by the measurement is defined as the BET specific surface area of the lithium titanium composite oxide in the present invention.

(2) Volume-based average particle diameter The volume-based average particle diameter of lithium-titanium composite oxide (secondary particle diameter when primary particles are aggregated to form secondary particles) is determined by laser diffraction / scattering method. It is defined by the obtained volume-based average particle diameter (median diameter).

  The volume-based average particle size of the lithium titanium composite oxide is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 0.7 μm or more, and usually 50 μm or less, preferably 40 μm or less, 30 μm. The following is more preferable, and 25 μm or less is particularly preferable.

  The volume-based average particle size is measured by dispersing a carbon powder in a 0.2% by mass aqueous solution (10 mL) of polyoxyethylene (20) sorbitan monolaurate, which is a surfactant, and a laser diffraction / scattering particle size distribution analyzer. (LA-700 manufactured by Horiba Ltd.) is used. The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material in the present invention.

  When the volume average particle size of the lithium titanium composite oxide is below the above range, a large amount of binder is required at the time of producing the electrode, and as a result, the battery capacity may decrease. On the other hand, if it exceeds the above range, an uneven coating surface tends to be formed when forming an electrode plate, which may be undesirable in the battery manufacturing process.

(3) Average primary particle diameter When primary particles are aggregated to form secondary particles, the average primary particle diameter of the lithium titanium composite oxide is usually 0.01 μm or more, and 0.05 μm or more. Preferably, it is 0.1 μm or more, more preferably 0.2 μm or more, and usually 2 μm or less, preferably 1.6 μm or less, more preferably 1.3 μm or less, and particularly preferably 1 μm or less. When the volume-based average primary particle diameter exceeds the above range, it is difficult to form spherical secondary particles, which adversely affects the powder filling property and the specific surface area greatly decreases. There is a possibility that performance is likely to deteriorate. On the other hand, below the above range, there are cases where the performance of the secondary battery is lowered, for example, reversibility of charge / discharge is inferior because crystals are underdeveloped.

  The primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at a magnification at which particles can be confirmed, for example, a magnification of 10,000 to 100,000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is determined for any 50 primary particles. Obtained and obtained by taking an average value.

(4) Shape As the shape of the lithium titanium composite oxide particles, a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, a column shape, etc., which are conventionally used, are used. Thus, it is preferable to form secondary particles, and the shape of the secondary particles is spherical or elliptical.

  In general, an electrochemical element expands and contracts as the active material in the electrode expands and contracts as it is charged and discharged. Therefore, the active material is easily damaged due to the stress or the conductive path is broken. Therefore, the primary particles are aggregated to form secondary particles rather than a single particle active material composed of only primary particles, so that the expansion and contraction stress is relieved and deterioration is prevented.

  In addition, spherical or oval spherical particles are less oriented during molding of the electrode than plate-like equiaxed particles, so there is less expansion and contraction of the electrode during charge and discharge, and an electrode is produced. The mixing with the conductive material is also preferable because it can be easily mixed uniformly.

(5) Tap Density Tap density lithium-titanium composite oxide is preferably from 0.05 g · ^{cm -3} or more, 0.1 g · ^{cm -3} or more, and more preferably 0.2 g · ^{cm -3} or more, 0.4 g · cm ⁻³ or more is particularly preferable, 2.8 g · cm ⁻³ or less is preferable, 2.4 g · cm ⁻³ or less is further preferable, and 2 g · cm ⁻³ or less is particularly preferable. When the tap density is less than the above range, the packing density is difficult to increase when used as a negative electrode, and the contact area between particles decreases, so that the resistance between particles increases and the output resistance may increase. On the other hand, if the above range is exceeded, the voids between the particles in the electrode may become too small, and the output resistance may increase due to a decrease in the flow path of the non-aqueous electrolyte solution.

The tap density is measured by passing through a sieve having an opening of 300 μm, dropping the sample onto a 20 cm ³ tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring device (for example, manufactured by Seishin Enterprise Co., Ltd.). Using a tap denser, tapping with a stroke length of 10 mm is performed 1000 times, and the density is calculated from the volume at that time and the weight of the sample. The tap density calculated by the measurement is defined as the tap density of the lithium titanium composite oxide in the present invention.

(6) Circularity When the circularity is measured as the spherical degree of the lithium titanium composite oxide, it is preferably within the following range. The circularity is defined as “circularity = (peripheral length of an equivalent circle having the same area as the particle projection shape) / (actual perimeter of the particle projection shape)”. It becomes.

  The circularity of the lithium-titanium composite oxide is preferably as close to 1, and is usually 0.10 or more, preferably 0.80 or more, more preferably 0.85 or more, and particularly preferably 0.90 or more. High current density charge / discharge characteristics improve as the circularity increases. Therefore, when the circularity is less than the above range, the filling property of the negative electrode active material is lowered, the resistance between particles is increased, and the high current density charge / discharge characteristics may be lowered for a short time.

  The circularity is measured using a flow type particle image analyzer (FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute. The detection range is specified as 0.6 to 400 μm, and the particle size is measured in the range of 3 to 40 μm. The circularity obtained by the measurement is defined as the circularity of the lithium titanium composite oxide in the present invention.

(7) Aspect ratio The aspect ratio of the lithium titanium composite oxide is usually 1 or more and usually 5 or less, preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. If the aspect ratio exceeds the above range, streaking or a uniform coated surface cannot be obtained when forming an electrode plate, and high current density charge / discharge characteristics may be deteriorated for a short time. The lower limit of the above range is the theoretical lower limit value of the aspect ratio of the lithium titanium composite oxide.

  The aspect ratio is measured by magnifying and observing lithium titanium composite oxide particles with a scanning electron microscope. Arbitrary 50 particles fixed on the end face of a metal having a thickness of 50 μm or less are selected, and the stage on which the sample is fixed is rotated and tilted for each, and the maximum particle size is obtained when three-dimensionally observed. The diameter A and the shortest diameter B perpendicular to it are measured, and the average value of A / B is obtained. The aspect ratio (A / B) determined by the measurement is defined as the aspect ratio of the lithium titanium composite oxide in the present invention.

(8) Method for producing negative electrode active material The method for producing lithium-titanium composite oxide is not particularly limited as long as it does not exceed the gist of the present invention. The method is used.

For example, a method of obtaining an active material by uniformly mixing a titanium source material such as titanium oxide and a source material of another element and a Li source such as LiOH, Li ₂ CO ₃ , or LiNO ₃ as necessary, and firing at a high temperature. Is mentioned.

In particular, various methods are conceivable for producing a spherical or elliptical active material. As an example, a titanium precursor material such as titanium oxide and, if necessary, a raw material material of another element are dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring to create a spherical precursor. There is a method in which the active material is obtained by recovering and drying it as necessary, and then adding a Li source such as LiOH, Li ₂ CO ₃ , or LiNO ₃ and baking at a high temperature.

As another example, a titanium raw material such as titanium oxide and, if necessary, a raw material of another element are dissolved or pulverized and dispersed in a solvent such as water. A method of obtaining an active material by adding a Li source such as LiOH, Li ₂ CO ₃ , LiNO _{3 and the} like to an elliptical spherical precursor and baking at a high temperature can be mentioned.

As yet another method, a titanium raw material such as titanium oxide, a Li source such as LiOH, Li ₂ CO ₃ and LiNO ₃ and a raw material of another element as necessary are dissolved or pulverized in a solvent such as water. There is a method in which it is dispersed and dried by a spray dryer or the like to obtain a spherical or elliptical precursor, which is then fired at a high temperature to obtain an active material.

  Also, during these steps, elements other than Ti, such as Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, C, Si, Sn , Ag may be present in the metal oxide structure containing titanium and / or in contact with the oxide containing titanium. By containing these elements, the operating voltage and capacity of the battery can be controlled.

(9) Electrode preparation Any known method can be used to manufacture the electrode. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.

  The thickness of the negative electrode active material layer per side in the stage immediately before the non-aqueous electrolyte injection process of the battery is usually 15 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and the upper limit is 150 μm or less, preferably 120 μm. Below, more preferably 100 μm or less. If it exceeds this range, the non-aqueous electrolyte solution hardly penetrates to the vicinity of the current collector interface, and thus the high current density charge / discharge characteristics may deteriorate. On the other hand, below this range, the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease. Further, the negative electrode active material may be roll-formed to form a sheet electrode, or may be formed into a pellet electrode by compression molding.

(10) Current collector As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as copper, nickel, aluminum, stainless steel, and nickel-plated steel. Among these, copper and aluminum are particularly preferable from the viewpoint of ease of processing and cost.

  The shape of the current collector includes, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, and a foam metal when the current collector is a metal material. Among them, a metal foil film containing copper (Cu) and / or aluminum (Al) is preferable, copper foil and aluminum foil are more preferable, rolled copper foil by a rolling method, and electrolytic copper by an electrolytic method are more preferable. There are foils, both of which can be used as current collectors.

  In addition, when the thickness of the copper foil is less than 25 μm, a copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) having higher strength than pure copper can be used. Moreover, since the specific gravity of aluminum foil is light, when it is used as a current collector, the weight of the battery can be reduced and can be preferably used.

  A current collector made of a copper foil produced by a rolling method is suitable for use in a small cylindrical battery because the copper crystals are arranged in the rolling direction so that the negative electrode is hard to crack even if it is rounded sharply or rounded at an acute angle. be able to.

  For example, an electrolytic copper foil is prepared by immersing a metal drum in an electrolytic solution in which copper ions are dissolved, and flowing current while rotating the copper drum, thereby depositing copper on the surface of the drum and peeling it off. It is obtained. Copper may be deposited on the surface of the rolled copper foil by an electrolytic method. One side or both sides of the copper foil may be subjected to a roughening treatment or a surface treatment (for example, a chromate treatment having a thickness of about several nm to 1 μm, a base treatment such as Ti).

Further, the following physical properties are desired for the current collector substrate.
(10-1) Average surface roughness (Ra)
The average surface roughness (Ra) of the active material thin film forming surface of the current collector substrate defined by the method described in JIS B0601-1994 is not particularly limited, but is usually 0.01 μm or more, preferably 0.03 μm or more. Further, it is usually 1.5 μm or less, preferably 1.3 μm or less, and more preferably 1.0 μm or less.

  This is because when the average surface roughness (Ra) of the current collector substrate is within the above range, good charge / discharge cycle characteristics can be expected. In addition, the area of the interface with the active material thin film is increased, and the adhesion with the negative electrode active material thin film is improved. The upper limit value of the average surface roughness (Ra) is not particularly limited, but those having an average surface roughness (Ra) exceeding 1.5 μm are generally available as foils having a practical thickness as a battery. Since it is difficult, those of 1.5 μm or less are usually used.

(10-2) Tensile strength Tensile strength is obtained by dividing the maximum tensile force required until the test piece breaks by the cross-sectional area of the test piece. The tensile strength in the present invention is measured by the same apparatus and method as described in JISZ2241 (metal material tensile test method).

The tensile strength of the current collector substrate is not particularly limited, is generally 50 N · ^{mm -2} or more, preferably 100 N · ^{mm -2} or more, more preferably 150 N · ^{mm -2} or more. The tensile strength is preferably as high as possible, but usually 1000 N · mm ⁻² or less is desirable from the viewpoint of industrial availability. If the current collector substrate has a high tensile strength, cracking of the current collector substrate due to expansion / contraction of the active material thin film accompanying charging / discharging can be suppressed, and good cycle characteristics can be obtained.

(10-3) 0.2% proof stress 0.2% proof stress is the size of a load necessary to give a plastic (permanent) strain of 0.2%. It means that 0.2% deformation has occurred even when loaded. The 0.2% yield strength is measured by the same apparatus and method as the tensile strength.

0.2% proof stress of the current collector substrate is not particularly limited, normally 30 N · ^{mm -2} or more, preferably 100 N · ^{mm -2} or more, particularly preferably 150 N · ^{mm -2} or more. The 0.2% proof stress is preferably as high as possible, but usually 900 N · mm ⁻² or less is desirable from the viewpoint of industrial availability. If the current collector substrate has a high 0.2% proof stress, plastic deformation of the current collector substrate due to expansion / contraction of the active material thin film accompanying charging / discharging can be suppressed, and good cycle characteristics can be obtained. This is because it can.

(10-4) Thickness of current collector Although the thickness of the current collector is arbitrary, it is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and usually 1 mm or less, 100 μm or less. Is preferably 30 μm or less. When the thickness of the current collector is thinner than 1 μm, the strength may be reduced, which may make application difficult. Moreover, when it becomes thicker than 100 micrometers, the shape of electrodes, such as winding, may be changed. The current collector may be mesh.

(11) Thickness ratio between current collector and active material layer The thickness ratio between the current collector and active material layer is not particularly limited, but “(the active material layer on one side immediately before non-aqueous electrolyte injection) The value of “thickness) / (current collector thickness)” is usually 150 or less, preferably 20 or less, more preferably 10 or less, and usually 0.1 or more, preferably 0.4 or more. One or more is more preferable. When the ratio of the thickness of the current collector to the negative electrode active material layer exceeds the above range, the current collector may generate heat due to Joule heat during high current density charge / discharge. On the other hand, below the above range, the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease.

(12) Electrode density The electrode structure when the negative electrode active material is converted into an electrode is not particularly limited, but the density of the active material present on the current collector is preferably 1 g · cm ⁻³ or more, and 1.2 g More preferably, cm ⁻³ or more, 1.3 g · cm ⁻³ or more is further preferable, 1.5 g · cm ⁻³ or more is particularly preferable, 3 g · cm ⁻³ or less is preferable, and 2.5 g · cm ^{−. 3} or less is more preferable, 2.2 g · cm ⁻³ or less is more preferable, and 2 g · cm ⁻³ or less is particularly preferable. When the density of the active material present on the current collector exceeds the above range, the binding between the current collector and the negative electrode active material becomes weak, and the electrode and the active material may be separated. On the other hand, below the above range, the conductivity between the negative electrode active materials may decrease, and the battery resistance may increase.

(13) Binder The binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte and the solvent used during electrode production.

  Specific examples include resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose; SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluororubber, Rubber polymers such as NBR (acrylonitrile / butadiene rubber) and ethylene / propylene rubber; styrene / butadiene / styrene block copolymer and hydrogenated products thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / styrene copolymers, styrene / isoprene / styrene block copolymers and hydrogenated products thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate , Soft resinous polymers such as ethylene / vinyl acetate copolymer, propylene / α-olefin copolymer; polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene / ethylene copolymer, etc. And a polymer composition having ion conductivity of alkali metal ions (particularly lithium ions). These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  The solvent for forming the slurry is not particularly limited as long as it is a solvent that can dissolve or disperse the negative electrode active material, binder, thickener and conductive material used as necessary. Alternatively, either an aqueous solvent or an organic solvent may be used.

  Examples of the aqueous solvent include water, alcohol and the like, and examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N , N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, dimethyl ether, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane and the like. In particular, when an aqueous solvent is used, a dispersant or the like is added in addition to the above-described thickener, and a slurry is formed using a latex such as SBR. In addition, these may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and usually 20% by mass or less, 15% by mass. % Or less is preferable, 10 mass% or less is more preferable, and 8 mass% or less is particularly preferable. When the ratio of the binder with respect to a negative electrode active material exceeds the said range, the binder ratio in which the amount of binders does not contribute to battery capacity may increase, and battery capacity may fall. On the other hand, if it is below the above range, the strength of the negative electrode is lowered, which may be undesirable in the battery production process.

  In particular, when a rubbery polymer represented by SBR is contained as a main component, the ratio of the binder to the active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, and 6 mass% or more is still more preferable, and it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is still more preferable.

  Further, when the main component contains a fluorine polymer represented by polyvinylidene fluoride, the ratio to the active material is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, Usually, it is 15 mass% or less, 10 mass% or less is preferable, and 8 mass% or less is still more preferable.

  A thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  Furthermore, when using a thickener, the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Moreover, it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is still more preferable. When the ratio of the thickener to the negative electrode active material is less than the above range, applicability may be significantly reduced. Moreover, when it exceeds the said range, the ratio of the active material which occupies for a negative electrode active material layer will fall, the problem that the capacity | capacitance of a battery falls, and the resistance between negative electrode active materials may increase.

<2-4. Positive electrode>
The positive electrode used for the non-aqueous electrolyte secondary battery of the present invention will be described below.

<2-4-1. Cathode active material>
The positive electrode active material used for the positive electrode will be described below.

(1) Composition The positive electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. For example, a material containing lithium and at least one transition metal is preferable. Specific examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds.

The transition metal of the lithium transition metal composite oxide is preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu or the like. Specific examples include lithium / cobalt composite oxide such as LiCoO ₂ and lithium such as LiNiO _2. Nickel composite oxide, LiMnO ₂ , LiMn ₂ O ₄ , Li ₂ MnO _{4 and} other lithium / manganese composite oxides, and some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti, Examples include those substituted with other metals such as V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, and Si.

As specific examples of the substituted ones, for example, LiNi _0.5 Mn _0.5 O ₂ , LiNi _0.85 Co _0.10 Al _0.05 O ₂ , LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , LiMn _1.8 Al _0.2 O ₄ , LiMn _1.5 Ni _0.5 O _{4 and the} like.

As the transition metal of the lithium-containing transition metal phosphate compound, V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable, and specific examples include, for example, LiFePO ₄ , Li ₃ Fe ₂ (PO ₄ ). ₃ , iron phosphates such as LiFeP ₂ O ₇ , cobalt phosphates such as LiCoPO ₄ , and some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn , Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other metals.

(2) Surface coating The surface of the positive electrode active material should have a material having a composition different from that of the main positive electrode active material (hereinafter abbreviated as “surface adhering material” as appropriate). You can also. Examples of surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, Examples thereof include sulfates such as calcium sulfate and aluminum sulfate, and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.

  These surface adhering substances are, for example, a method in which they are dissolved or suspended in a solvent and impregnated and added to the positive electrode active material and then dried, or a surface adhering substance precursor is dissolved or suspended in a solvent and impregnated and added to the positive electrode active material. Then, it can be made to adhere to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing simultaneously.

  The mass of the surface adhering material adhering to the surface of the positive electrode active material is usually 0.1 ppm or more, preferably 1 ppm or more, more preferably 10 ppm or more, and usually 20% with respect to the mass of the positive electrode active material. Or less, preferably 10% or less, more preferably 5% or less.

  The surface adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte on the surface of the positive electrode active material, and can improve the battery life. However, when the adhesion amount is less than the above range, the effect is not sufficiently exhibited. When the adhesion amount is more than the above range, the resistance may increase in order to inhibit the entry / exit of lithium ions, so the above range is preferable.

(3) Shape As the shape of the positive electrode active material particles, a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, a column shape, etc., which are conventionally used, are used. It is preferable to form secondary particles, and the shape of the secondary particles is spherical or elliptical.

  In general, an electrochemical element expands and contracts as the active material in the electrode expands and contracts as it is charged and discharged. Therefore, the active material is easily damaged due to the stress or the conductive path is broken. Therefore, the primary particles are aggregated to form secondary particles rather than a single particle active material having only primary particles, so that the stress of expansion and contraction is relieved and deterioration is prevented.

  In addition, spherical or oval spherical particles are less oriented at the time of forming the electrode than the plate-like equiaxially oriented particles, so there is less expansion and contraction of the electrode during charge and discharge, and when creating the electrode Also in the mixing with the conductive material, it is preferable because it is easily mixed uniformly.

(4) Tap density The tap density of the positive electrode active material is usually 1.3 g · cm ⁻³ or more, preferably 1.5 g · cm ⁻³ or more, more preferably 1.6 g · cm ⁻³ or more. 7 g · cm ⁻³ or more is particularly preferable, usually 3 g · cm ⁻³ or less, and preferably 2.5 g · cm ⁻³ or less.

  By using a metal composite oxide powder having a high tap density, a high-density positive electrode active material layer can be formed. Therefore, when the tap density of the positive electrode active material is lower than the above range, the amount of the dispersion medium necessary for forming the positive electrode active material layer increases, and the necessary amount of the conductive material and the binder increases. The filling rate of the positive electrode active material is limited, and the battery capacity may be limited. In general, the tap density is preferably as large as possible, but there is no particular upper limit. However, if the tap density is below the above range, diffusion of lithium ions in the positive electrode active material layer as a medium becomes rate-determining and load characteristics are likely to deteriorate. There is a case.

The tap density is measured by passing a sieve having an opening of 300 μm, dropping the sample onto a 20 cm ³ tapping cell to fill the cell volume, and then using a powder density measuring instrument (for example, a tap denser manufactured by Seishin Enterprise Co., Ltd.). The tapping with a stroke length of 10 mm is performed 1000 times, and the density is calculated from the volume at that time and the weight of the sample. The tap density calculated by the measurement is defined as the tap density of the positive electrode active material in the present invention.

(5) Median diameter d50
The median diameter d50 (secondary particle diameter when primary particles are aggregated to form secondary particles) of the positive electrode active material particles should also be measured using a laser diffraction / scattering particle size distribution analyzer. Can do.

  The median diameter d50 is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, particularly preferably 3 μm or more, and usually 20 μm or less, preferably 18 μm or less, more preferably 16 μm or less. 15 μm or less is particularly preferable. If the median diameter d50 is below the above range, a high bulk density product may not be obtained. If the median diameter d50 is above the above range, it takes time to diffuse lithium in the particles. That is, when an active material, a conductive material, a binder, or the like is slurried with a solvent and applied as a thin film, streaks may occur.

  In addition, the filling property at the time of positive electrode preparation can be further improved by mixing two or more types of positive electrode active materials having different median diameters d50 at an arbitrary ratio.

  The median diameter d50 is measured by using a 0.1% by mass sodium hexametaphosphate aqueous solution as a dispersion medium, and using LA-920 manufactured by HORIBA, Ltd. as a particle size distribution meter, the refractive index is adjusted to 1.24 after ultrasonic dispersion for 5 minutes. Set and measure.

(6) Average primary particle diameter When primary particles aggregate to form secondary particles, the average primary particle diameter of the positive electrode active material is usually 0.01 μm or more, preferably 0.05 μm or more, and It is more preferably at least 08 μm, particularly preferably at least 0.1 μm, usually not more than 3 μm, preferably not more than 2 μm, more preferably not more than 1 μm, particularly preferably not more than 0.6 μm. If the above range is exceeded, it may be difficult to form spherical secondary particles, which may adversely affect the powder filling property, or the specific surface area will be greatly reduced, which may increase the possibility that the battery performance such as output characteristics will deteriorate. Because there is. Further, if the value is below the above range, the performance of the secondary battery may be deteriorated, for example, the reversibility of charge / discharge is inferior because the crystal is not developed.

  The average primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles and obtained by taking the average value. It is done.

(7) BET specific surface area As for the BET specific surface area of the positive electrode active material, the value of the specific surface area measured using the BET method is usually 0.2 m ² · g ⁻¹ or more, and 0.3 m ² · g ⁻¹ or more. 0.4 m ² · g ⁻¹ or more is more preferable, usually 4.0 m ² · g ⁻¹ or less, preferably 2.5 m ² · g ⁻¹ or less, and 1.5 m ² · g ^{−. 1} or less is more preferable. When the value of the BET specific surface area is below the above range, the battery performance tends to be lowered. Moreover, when it exceeds the said range, a tap density becomes difficult to raise and the applicability | paintability at the time of positive electrode active material formation may fall.

  The BET specific surface area is measured using a surface area meter (a fully automatic surface area measuring device manufactured by Okura Riken). The sample was preliminarily dried at 150 ° C. for 30 minutes under a nitrogen flow, and then a nitrogen helium mixed gas that was accurately adjusted so that the relative pressure of nitrogen with respect to atmospheric pressure was 0.3 was used. It is measured by the nitrogen adsorption BET one-point method by the flow method. The specific surface area determined by the measurement is defined as the BET specific surface area of the anode active material in the present invention.

(8) Method for Producing Positive Electrode Active Material The method for producing the positive electrode active material is not particularly limited as long as it does not exceed the gist of the present invention, but there are several methods, which are common as methods for producing inorganic compounds. The method is used.

In particular, various methods are conceivable for producing a spherical or elliptical active material. For example, transition metal source materials such as transition metal nitrates and sulfates, and other element source materials as required. Is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring to produce and recover a spherical precursor, which is dried as necessary, and then LiOH, Li ₂ CO ₃ , LiNO There is a method in which an active material is obtained by adding a Li source such as ₃ and baking at a high temperature.

In addition, as an example of another method, transition metal raw materials such as transition metal nitrates, sulfates, hydroxides, oxides and the like, and if necessary, raw materials of other elements are dissolved or pulverized and dispersed in a solvent such as water. Then, it is dry-molded with a spray dryer or the like to obtain a spherical or elliptical precursor, and a Li source such as LiOH, Li ₂ CO ₃ , LiNO ₃ is added to the precursor and calcined at a high temperature to obtain an active material Is mentioned.

Examples of other methods include transition metal source materials such as transition metal nitrates, sulfates, hydroxides, oxides, Li sources such as LiOH, Li ₂ CO ₃ , LiNO ₃ , and other elements as necessary. The raw material is dissolved or pulverized and dispersed in a solvent such as water, and is then dried by a spray dryer or the like to form a spherical or elliptical precursor, which is fired at a high temperature to obtain an active material. Can be mentioned.

<2-4-2. Electrode structure and fabrication method>
Below, the structure of the positive electrode used for this invention and its preparation method are demonstrated.

(1) Method for Producing Positive Electrode The positive electrode is produced by forming a positive electrode active material layer containing positive electrode active material particles and a binder on a current collector. The production of the positive electrode using the positive electrode active material can be produced by any known method. That is, a positive electrode active material and a binder, and if necessary, a conductive material and a thickener mixed in a dry form are pressure-bonded to a positive electrode current collector, or these materials are liquid media A positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying it to a positive electrode current collector and drying it as a slurry by dissolving or dispersing in a slurry.

  The content of the positive electrode active material in the positive electrode active material layer is usually 10% by mass or more, preferably 30% by mass or more, particularly preferably 50% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass. It is as follows. This is because if the content of the positive electrode active material in the positive electrode active material layer is less than the above range, the electric capacity may be insufficient. Moreover, it is because the intensity | strength of a positive electrode may be insufficient when it exceeds the said range. In addition, the positive electrode active material powder in this invention may be used individually by 1 type, and may use together 2 or more types of a different composition or different powder physical properties by arbitrary combinations and ratios.

(2) Conductive material As the conductive material, a known conductive material can be arbitrarily used. Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbonaceous materials such as amorphous carbon such as needle coke. . In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The conductive material is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less in the positive electrode active material layer. More preferably, it is used so as to contain 15% by mass or less. If the content is lower than the above range, the conductivity may be insufficient. Moreover, when it exceeds the said range, battery capacity may fall.

(3) Binder The binder used in the production of the positive electrode active material layer is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used during electrode production.

  In the case of the coating method, any material can be used as long as it is dissolved or dispersed in the liquid medium used during electrode production. Specific examples include, for example, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, and cellulose. Resin polymers such as nitrocellulose; rubbery polymers such as SBR (styrene butadiene rubber), NBR (acrylonitrile butadiene rubber), fluoro rubber, isoprene rubber, butadiene rubber, ethylene propylene rubber; styrene butadiene Styrene block copolymer or hydrogenated product thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / butadiene / ethylene copolymer, styrene / isoprene / styrene block copolymer or hydrogenated product thereof Etc. heat Plastic elastomeric polymers: Syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene / vinyl acetate copolymers, propylene / α-olefin copolymers, etc .; polyvinylidene fluoride (PVdF) , Fluorine-based polymers such as polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene / ethylene copolymers; polymer compositions having ion conductivity of alkali metal ions (particularly lithium ions), and the like. . These substances may be used alone or in combination of two or more in any combination and ratio.

  The ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and usually 80% by mass or less, and 60% by mass. % Or less is preferable, 40% by mass or less is more preferable, and 10% by mass or less is particularly preferable. When the ratio of the binder is below the above range, the positive electrode active material cannot be sufficiently retained, the positive electrode has insufficient mechanical strength, and battery performance such as cycle characteristics may be deteriorated. Moreover, when it exceeds the said range, it may lead to a battery capacity or electroconductivity fall.

(4) Liquid medium The liquid medium for forming the slurry may be a solvent capable of dissolving or dispersing the positive electrode active material, the conductive material, the binder, and the thickener used as necessary. For example, the type is not particularly limited, and either an aqueous solvent or an organic solvent may be used.

  Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like. Examples of organic media include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone. Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) and dimethylformamide And amides such as dimethylacetamide; aprotic polar solvents such as hexamethylphosphalamide and dimethyl sulfoxide. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(5) Thickener When using an aqueous medium as a liquid medium for forming a slurry, it is preferable to make a slurry using a thickener and a latex such as styrene butadiene rubber (SBR). A thickener is usually used to adjust the viscosity of the slurry.

  The thickener is not limited as long as the effect of the present invention is not significantly limited. Specifically, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and salts thereof Etc. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.

  Further, when using a thickener, the ratio of the thickener to the active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Usually, it is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. If it falls below the above range, applicability may be remarkably reduced, and if it exceeds the above range, the ratio of the active material in the positive electrode active material layer is lowered, the battery capacity is reduced, and the resistance between the positive electrode active materials. May increase.

(6) Consolidation The positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material. The density of the positive electrode active material layer is preferably 1 g · cm ⁻³ or more, more preferably 1.5 g · cm ⁻³ or more, and particularly preferably 2 g · cm ⁻³ or more. The upper limit is preferably 4g · ^{cm -3} or less, 3.5 g · ^{cm -3} or less is more preferable. When the density of the positive electrode active material layer exceeds the above range, the permeability of the non-aqueous electrolyte solution to the vicinity of the current collector / active material interface may decrease, and the charge / discharge characteristics at a high current density may decrease. . Moreover, when less than the said range, the electroconductivity between active materials may fall and battery resistance may increase.

(7) Current collector The material of the positive electrode current collector is not particularly limited, and known materials can be arbitrarily used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbonaceous materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.

  Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, foam metal, etc. A carbon thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred. In addition, you may form a thin film suitably in mesh shape.

  The thickness of the current collector is arbitrary, but is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and usually 1 mm or less, preferably 100 μm or less, more preferably 50 μm or less. If the thin film is thinner than the above range, the strength required for the current collector may be insufficient. Moreover, when a thin film is thicker than the said range, a handleability may be impaired.

<2-5. Separator>
Usually, a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.

  There is no restriction | limiting in particular about the material and shape of a separator, As long as the effect of this invention is not impaired remarkably, a well-known thing can be employ | adopted arbitrarily. Among them, a resin, glass fiber, inorganic material, etc. formed of a material that is stable with respect to the non-aqueous electrolyte solution of the present invention is used, and a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties is used. Is preferred.

  As materials for the resin and the glass fiber separator, for example, polyolefins such as polyethylene and polypropylene, polytetrafluoroethylene, polyethersulfone, glass filters and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The thickness of the separator is arbitrary, but is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less. If the separator is too thin than the above range, the insulating properties and mechanical strength may decrease. On the other hand, if it is thicker than the above range, not only the battery performance such as the rate characteristic may be lowered, but also the energy density of the whole non-aqueous electrolyte secondary battery may be lowered.

  Furthermore, when a porous material such as a porous sheet or nonwoven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Moreover, it is 90% or less normally, 85% or less is preferable and 75% or less is still more preferable. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.

  Moreover, although the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, 0.2 micrometer or less is preferable, and it is 0.05 micrometer or more normally. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.

  On the other hand, as inorganic materials, for example, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used. Things are used.

  As the form, a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 to 1 μm and a thickness of 5 to 50 μm are preferably used. In addition to the independent thin film shape, a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, a porous layer may be formed by using alumina particles having a 90% particle size of less than 1 μm on both surfaces of the positive electrode and using a fluororesin as a binder.

<2-6. Battery design>
[Electrode group]
The electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed via the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape via the separator. Either may be used. The ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupation ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. . When the electrode group occupancy is below the above range, the battery capacity decreases. Also, if the above range is exceeded, the void space is small, the battery expands, and the member expands or the vapor pressure of the electrolyte liquid component increases and the internal pressure rises. In some cases, a gas release valve that lowers various characteristics such as storage at high temperature and the like, or releases the internal pressure to the outside is activated.

[Current collection structure]
The current collecting structure is not particularly limited, but it is preferable to have a structure that reduces the resistance of the wiring part and the joint part.

  In the case where the electrode group has the laminated structure described above, a structure formed by bundling the metal core portions of the electrode layers and welding them to the terminals is preferably used. When the area of one electrode increases, the internal resistance increases. Therefore, it is also preferable to reduce the resistance by providing a plurality of terminals in the electrode. When the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures for the positive electrode and the negative electrode, respectively, and bundling the terminals.

[Exterior case]
The material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used. The shape of the outer case is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

  In the exterior case using the above metals, a laser-sealed, resistance-welded, ultrasonic welding is used to weld the metals together to form a sealed sealed structure, or a caulking structure using the above-mentioned metals via a resin gasket To do. Examples of the outer case using the laminate film include those having a sealed and sealed structure by heat-sealing resin layers. In order to improve the sealing performance, a resin different from the resin used for the laminate film may be interposed between the resin layers. In particular, when a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used. Resins are preferably used.

[Protective element]
As a protective element, PTC (Positive Temperature Coefficient), thermal fuse, thermistor, whose resistance increases when abnormal heat or excessive current flows, cut off current flowing in the circuit due to sudden rise in battery internal pressure or internal temperature at abnormal heat generation And the like (current cutoff valve). It is preferable to select a protective element that does not operate under normal use at a high current. From the viewpoint of high output, it is more preferable to design the protective element so as not to cause abnormal heat generation or thermal runaway even without the protective element.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.

Each evaluation method of the non-aqueous electrolyte secondary battery obtained in the following examples and comparative examples is shown below.
<Measurement of initial discharge capacity>
The non-aqueous electrolyte secondary battery is charged to 4.2 V at a constant current corresponding to 0.2 C at 25 ° C. in a state of being sandwiched between glass plates in order to improve the adhesion between the electrodes, and then 0.2 C The battery was discharged to 3 V at a constant current of. This is done for 3 cycles to stabilize the battery. In the 4th cycle, after charging to 4.2V with a constant current of 0.5C, charging is performed until the current value reaches 0.05C with a constant voltage of 4.2V. The initial discharge capacity was determined by discharging to 3 V at a constant current of 0.2C. Here, 1C represents a current value for discharging the reference capacity of the battery in one hour, and 0.2C represents a current value of 1/5 thereof.

<Evaluation of continuous charging characteristics>
After the capacity evaluation test was completed, the non-aqueous electrolyte secondary battery was immersed in an ethanol bath and the volume was measured. Then, the battery was charged at a constant current of 0.5 C at 60 ° C. and reached 4.25 V. Then, it switched to the constant voltage charge and performed the continuous charge for one week. After cooling the battery, the volume was measured by immersing in an ethanol bath, and the amount of gas generated from the volume change before and after continuous charging was determined, and this was defined as “the amount of generated gas after continuous charging (mL)”. After measurement of the amount of generated gas, it was discharged to 3 V at a constant current of 0.2 C at 25 ° C. Next, after charging to 4.2 V at a constant current of 0.5 C, charging is performed until the current value reaches 0.05 C at a constant voltage of 4.2 V, and then discharged to 3 V at a constant current of 1 C. The 1C discharge capacity after the charge test was measured. The ratio of the 1C discharge capacity after the continuous charge test to the initial discharge capacity was determined, and this was defined as “1C discharge capacity (%) after continuous charge”.

Example 1
<Preparation of non-aqueous electrolyte secondary battery>
[Production of negative electrode]
The d value of the lattice plane (002 plane) in X-ray diffraction is 0.336 nm, the crystallite size (Lc) is 652 nm, the ash content is 0.07 parts by weight, the median diameter by laser diffraction / scattering method is 12 μm, the ratio by BET method The half-value width of a peak whose surface area is 7.5 m ² / g and the R value (= I _B / I _A ) determined from Raman spectrum analysis using an argon ion laser beam is in the range of 0.12, 1570 to 1620 cm ^−1. Was mixed with 94 parts by weight of natural graphite powder having a weight of 19.9 cm ⁻¹ and 6 parts by weight of polyvinylidene fluoride, and N-methyl-2-pyrrolidone was added to form a slurry. This slurry was uniformly applied to one side of a 12 μm thick copper foil and dried, and then pressed to obtain a negative electrode active material layer having a density of 1.67 g / cm ³ to form a negative electrode.

[Production of positive electrode]
90% by mass of lithium cobaltate (LiCoO ₂ ) as a positive electrode active material, 4% by mass of carbon black, and 6% by mass of polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd., trade name “KF-1000”) are mixed, and N-methyl 2-Pyrrolidone was added to form a slurry, which was applied to both sides of an aluminum foil having a thickness of 15 μm, dried, and then pressed so that the density of the positive electrode active material layer was 3.2 g / cm ³ to obtain a positive electrode.

[Non-aqueous electrolyte]
Under a dry argon atmosphere, a mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (volume ratio 2: 4: 4), fully dried LiPF ₆ at 1 mol / L, vinylene carbonate at 2% by mass, monofluorophosphoric acid The salt and / or difluorophosphate and “the compound of the present invention” were dissolved so as to have predetermined concentrations shown in Table 1, respectively, to obtain a desired nonaqueous electrolytic solution.

[Manufacture of non-aqueous electrolyte secondary batteries]
The positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, the positive electrode, the separator, and the negative electrode to produce a battery element. The battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 μm) were coated with a resin layer while projecting positive and negative terminals, and then the electrolyte was poured into the bag and vacuum sealed. The sheet-like battery was fabricated and the above-described continuous charge characteristics were evaluated. The results are shown in Table 1.

Examples 2 to 10, Comparative Examples 1 to 4
Example 1 except that the “monofluorophosphate and / or difluorophosphate” and “compound in the present invention” described in Table 1 were used in place of the types and contents described in Table 1. Similarly, a desired non-aqueous electrolyte solution was prepared, and after the production of the non-aqueous electrolyte secondary battery, the continuous charge characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As is apparent from Table 1, the non-aqueous electrolyte solution of the present invention contains the “compound of the present invention” and contains a monofluorophosphate and / or difluorophosphate. In the non-aqueous electrolyte secondary battery produced by using (Example 1 to Example 10), a non-aqueous electrolyte containing one of these compounds (Comparative Example 2 to Comparative Example 4), or both of these compounds are used. Compared with a non-aqueous electrolyte secondary battery prepared using a non-aqueous electrolyte solution that does not contain (Comparative Example 1), gas generation during continuous charging and deterioration of battery characteristics were suppressed.

  According to the non-aqueous electrolyte solution of the present invention, it is possible to produce a non-aqueous electrolyte solution and a non-aqueous electrolyte secondary battery excellent in cycle characteristics, storage characteristics, gas generation suppression during continuous charging, and battery characteristics. Therefore, it can be suitably used in various fields such as an electronic device in which a non-aqueous electrolyte secondary battery is used.

  The use of the non-aqueous electrolyte for secondary batteries and the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be used for various known applications. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, and transceivers. Electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, automobiles, motorcycles, motorbikes, bicycles, lighting equipment, toys, game equipment, watches, electric tools, strobes, cameras, etc. Can do.

Claims (4)

A nonaqueous electrolytic solution mainly composed of an electrolyte and a nonaqueous solvent that dissolves the electrolyte, containing a monofluorophosphate and / or difluorophosphate, and a compound represented by the general formula (1), a nitrile compound , An isocyanate compound, a phosphazene compound, a disulfonic acid ester compound, a sulfide compound, a disulfide compound, an acid anhydride, a lactone compound having a substituent at the α-position, and at least one selected from the group having a carbon-carbon triple bond A non-aqueous electrolyte containing the following compound.

[In General Formula (1), R ¹ , R ² and R ³ are each independently substituted with a fluorine atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. The C1-C12 alkoxy group which may be represented. ]   2. The nonaqueous electrolytic solution according to claim 1, wherein the total content of monofluorophosphate and / or difluorophosphate is 0.01 wt% or more and 5 wt% or less of the entire nonaqueous electrolytic solution.   Compound represented by general formula (1), nitrile compound, isocyanate compound, phosphazene compound, disulfonic acid ester compound, sulfide compound, disulfide compound, acid anhydride, lactone compound having a substituent at α-position, carbon-carbon triple bond 3. The non-aqueous electrolyte solution according to claim 1, wherein the total content of the compounds selected from the group consisting of compounds having a non-aqueous electrolyte solution is 0.01% by mass or more and 25% by mass or less of the entire non-aqueous electrolyte solution. .   A non-aqueous electrolyte secondary battery comprising at least a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is any one of claims 1 to 3. A non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte solution according to claim 1.