JP5708597B2 - Non-aqueous electrolyte for lithium ion secondary battery and lithium ion secondary battery - Google Patents

Description

The present invention relates to a non-aqueous electrolyte for a lithium ion secondary battery and a lithium ion secondary battery.

  Lithium ion secondary batteries are lighter and have higher capacity than nickel cadmium batteries and nickel metal hydride batteries, and thus are widely applied as power sources for portable electronic devices. It is also a promising candidate as a power source for hybrid vehicles and electric vehicles. However, with the recent miniaturization and higher functionality of portable electronic devices, further increase in capacity is expected for lithium ion secondary batteries serving as these power sources.

  A lithium ion secondary battery is mainly composed of a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte. Generally, a lithium metal composite oxide is used for the positive electrode, and a carbon material that can occlude and release lithium ions is used for the negative electrode. A liquid electrolyte in which a lithium salt is dissolved in an organic solvent that is liquid at room temperature is used as a non-aqueous electrolyte. However, a side reaction involving an organic solvent occurs on the surface of the carbon material of the negative electrode, which adversely affects the characteristics such as an expected discharge capacity cannot be obtained. For this reason, it is an important issue to form a film on the surface of the negative electrode and to control the state and properties of the film so that the negative electrode does not directly react with the organic solvent.

  In order to form and control this negative electrode surface film, a special additive is added to the non-aqueous electrolyte. For example, it has been clarified that cycle characteristics are improved by adding fluoroethylene carbonate to a non-aqueous electrolyte (see Patent Document 1). The addition of fluoroethylene carbonate is considered to result from the formation of a film on the surface of the negative electrode and the suppression of side reactions on the negative electrode. In the following, the non-aqueous electrolyte for a lithium ion secondary battery is referred to as a non-aqueous electrolyte depending on the case.

Japanese Patent Laid-Open No. 7-240232

  However, in the conventional lithium ion secondary battery described in Patent Document 1 described above, an unnecessary reaction or decomposition of the electrolytic solution is suppressed by forming a film on the negative electrode surface, and a low-temperature cycle at room temperature and 0 ° C. Although an improvement in characteristics was confirmed, significant capacity deterioration was observed during a charge / discharge cycle at a high temperature of 45 ° C. In addition, a sufficient discharge capacity cannot be obtained during discharge at a low temperature of less than 0 ° C., and various characteristics necessary for a secondary battery cannot be satisfied at the same time.

  The present invention has been made in view of the above problems, and provides a non-aqueous electrolyte for a lithium ion secondary battery and a lithium ion secondary battery that can obtain a sufficient discharge capacity even at a low temperature and has good high-temperature cycle characteristics. The purpose is to provide.

  The non-aqueous electrolyte for a lithium ion secondary battery of the present invention includes a non-aqueous solvent and an electrolyte, 0.05 to 4% by mass of fluoroethylene carbonate, 0.001 to 0.5% by mass of cyclic ether, It is characterized by including.

  Both fluoroethylene carbonate and cyclic ether contribute to the formation of a film in a wide temperature range at the interface between the negative electrode of the lithium ion secondary battery and the non-aqueous electrolyte. By setting the contents of fluoroethylene carbonate and cyclic ether within the specified ranges, a lithium ion battery having a high lithium ion conductivity and a sufficient discharge capacity can be obtained even at low temperatures. Further, it is considered that this coating can realize an excellent discharge capacity even after a charge / discharge cycle at a high temperature by suppressing side effects such as decomposition of the nonaqueous solvent.

  The cyclic ether in the non-aqueous electrolyte for a lithium ion secondary battery of the present invention is preferably 1,4-dioxane. Thereby, the lithium ion conductivity at a low temperature is increased, and a higher discharge capacity can be obtained.

  The non-aqueous electrolyte for a lithium ion secondary battery of the present invention preferably contains ethylene carbonate and ethyl methyl carbonate as a non-aqueous solvent. Ethylene carbonate and ethyl methyl carbonate are a combination suitable for simultaneously improving the discharge capacity at low temperature and the cycle characteristics at high temperature.

Since the nonaqueous electrolytic solution for a lithium ion secondary battery of the present invention has high conductivity even at a low temperature and a sufficient discharge capacity can be obtained, the electrolyte preferably contains LiPF ₆ .

〔式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に水素原子及び炭素数１〜５の炭化水素基からなる群より選ばれる少なくとも一種を表す。〕 The non-aqueous electrolyte for a lithium ion secondary battery of the present invention preferably further contains 4% by mass or less of an ethylene glycol sulfate derivative represented by the following formula (1).

[In Formula (1), R < ₁ > and R < ₂ > represents at least 1 type chosen from the group which consists of a hydrogen atom and a C1-C5 hydrocarbon group each independently. ]

  The ethylene glycol sulfate derivative, together with fluoroethylene carbonate and cyclic ether, contributes to film formation at the interface between the negative electrode active material of the lithium ion secondary battery and the non-aqueous electrolyte. By containing an appropriate amount of the glycol sulfate derivative, the internal impedance of the lithium ion secondary battery can be further reduced, and the discharge capacity at a low temperature can be further increased. In addition, since the formed film is further strengthened, it is expected that the cycle characteristics at high temperatures are further improved.

The ethylene glycol sulfate derivative represented by the formula (1) is preferably an ethylene glycol sulfate in which R ₁ and R ₂ are both hydrogen atoms from the viewpoint of improving high-temperature cycle characteristics.

  The lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution. The non-aqueous electrolyte solution includes 0.01 to 4 mass of a non-aqueous solvent, an electrolyte, and fluoroethylene carbonate. % And cyclic ether in an amount of 0.001 to 0.5 mass%.

  The negative electrode of the lithium ion secondary battery of the present invention preferably contains a carbon material as a main component.

  According to the present invention, it is possible to provide a non-aqueous electrolyte for a lithium ion secondary battery and a lithium ion secondary battery that can obtain a sufficient discharge capacity even at a low temperature and have good cycle characteristics even at a high temperature.

It is a schematic cross section of a lithium ion secondary battery.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the non-aqueous electrolyte for lithium ion secondary batteries and the lithium ion secondary battery according to the present invention are not limited to the following embodiments. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.

(Lithium ion secondary battery)
Next, the electrode and the lithium ion secondary battery according to this embodiment will be briefly described with reference to FIG.

  The lithium ion secondary battery 100 mainly includes a power generation element 30, a case 50 that houses the power generation element 30 in a sealed state, and a pair of leads 60 and 62 connected to the power generation element 30.

  The power generation element 30 is configured such that a pair of electrodes 10 and 20 are disposed to face each other with the separator 18 interposed therebetween. The positive electrode 10 is a product in which a positive electrode active material layer 14 is provided on a positive electrode current collector 12. The negative electrode 20 is a product in which a negative electrode active material layer 24 is provided on a negative electrode current collector 22. The positive electrode active material layer 14 and the negative electrode active material layer 24 are in contact with both sides of the separator 18. The positive electrode active material layer 14, the negative electrode active material layer 24, and the separator 18 contain an electrolyte solution. Leads 60 and 62 are connected to the end portions of the positive electrode current collector 12 and the negative electrode current collector 22, respectively, and the end portions of the leads 60 and 62 extend to the outside of the case 50.

(Negative electrode)
The negative electrode 20 includes a negative electrode active material layer 24 on both sides of a negative electrode current collector 22. Furthermore, the negative electrode active material layer 24 is formed by applying a paint containing a negative electrode active material, a conductive additive, and a binder to the negative electrode current collector 22.

The negative electrode active material includes at least one selected from carbon materials such as natural graphite, artificial graphite (non-graphitizable carbon, graphitizable carbon, low-temperature calcined carbon, etc.), MCF (mesocarbon fiber), and the like. Among these, artificial graphite is preferable because it exhibits a favorable negative electrode capacity and cycle characteristics, and from the viewpoint of improving electrode density, it is more preferable to use artificial graphite mixed with natural graphite. In addition, for example, a metal capable of forming a compound with lithium such as Al, Si and Sn, an amorphous compound mainly composed of an oxide such as SiO ₂ and SnO ₂ , lithium titanate (Li ₄ Ti ₅ O _A known negative electrode active material such as ₁₂ ) may be mixed with a carbon material.

  The conductive auxiliary agent is not particularly limited, and a known conductive auxiliary agent can be used. Examples thereof include carbon materials such as pyrolytic carbon such as carbon black, cokes, glassy carbons, organic polymer compound fired materials, carbon fibers, and activated carbon. Moreover, you may add negative electrode active material materials, such as non-graphitizable carbon, easily graphitizable carbon, and graphite, changing a shape.

  As carbon black, acetylene black, ketjen black and the like are particularly preferable, and ketjen black is particularly preferable. By including an electron-conductive porous body, pores can be formed at the interface between the particles of the negative electrode active material and the binder, and the penetration of the non-aqueous electrolyte into the negative electrode active material layer 24 is facilitated by the pores. This is preferable.

  The binder is not particularly limited as long as it can bind the negative electrode active material particles and the conductive auxiliary particles. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoro Examples thereof include fluorine resins such as ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). Further, the binder contributes not only to the binding of the particles of the negative electrode active material material and the particles of the conductive additive but also the binding to the negative electrode current collector 22.

  As the negative electrode current collector 22, various known metal foils used for current collectors for lithium ion secondary batteries can be used. Specifically, it is preferable to use a copper foil.

(Positive electrode)
The positive electrode 10 includes a positive electrode active material layer 14 on both surfaces of a positive electrode current collector 12. Furthermore, the positive electrode active material layer 14 is formed by applying a paint containing a positive electrode active material, a conductive additive, and a binder to the positive electrode current collector 12.

The positive electrode active material is composed of lithium ion occlusion and release, lithium ion desorption and insertion (intercalation), or doping and dedoping of a lithium ion and a counter anion (for example, ClO ₄ ⁻ ) of the lithium ion. Is not particularly limited as long as it can reversibly proceed, and a known electrode active material can be used. For example, lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganese spinel (LiMn ₂ O ₄ ), general formula: LiNi _x Co _y Mn _z O ₂ (x + y + z = 1) or Li _a Ni _x Co _y Al _1-xy O ₂ (0.98 <a <1.2, 0 <x, y <1) A composite metal oxide, olivine-type LiMPO ₄ (where M is Co, Ni , Mn, Fe or V), and composite metal oxides such as lithium vanadium compounds (LiVOPO ₄ ).

  Furthermore, each constituent element (conductive auxiliary agent and binder) other than the positive electrode active material can use the same substances as those used in the negative electrode 20. Therefore, the binder contained in the positive electrode 10 contributes not only to the binding between the particles of the positive electrode active material and the particles of the conductive auxiliary agent, but also to the binding to the positive electrode current collector 12. Yes.

  As the positive electrode current collector 12, various known metal foils used in current collectors for lithium ion secondary batteries can be used. Specifically, it is preferable to use an aluminum foil.

(Separator)
As long as the separator 18 is formed of an insulating porous material, the material, the manufacturing method, and the like are not particularly limited, and a known separator used in the lithium ion secondary battery 100 can be used. For example, as the insulating porous material, a known polyolefin resin, specifically, a crystalline homopolymer or copolymer obtained by polymerizing polyethylene, polypropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, or the like. A polymer is mentioned. These homopolymers or copolymers can be used alone or in combination of two or more. Further, it may be a single layer or a multilayer.

(Nonaqueous electrolyte)
The nonaqueous electrolytic solution contains a nonaqueous solvent, an electrolyte, 0.05 to 4% by mass of fluoroethylene carbonate, and 0.001 to 0.5% by mass of cyclic ether.

  Although the mechanism of the effect expression by simultaneously containing fluoroethylene carbonate and cyclic ether in the nonaqueous electrolytic solution is not clear, the present inventors consider as follows.

  Fluoroethylene carbonate forms a film on the surface of the negative electrode active material layer 24, and the film mainly works effectively for cycle characteristics. At the same time, a film is formed on the surface of the positive electrode active material layer 14, and energy required when lithium ions are inserted into the positive electrode active material layer 14 is reduced. Therefore, the lithium ion secondary battery 100 containing fluoroethylene carbonate often has improved high rate discharge characteristics and low temperature discharge characteristics. However, these coatings are fragile when heated to high temperatures. In particular, in charge / discharge cycle tests at high temperatures, the nonaqueous electrolyte reacts and decomposes with the positive electrode active material or negative electrode active material, and gas is generated. The discharge capacity is also reduced.

  Therefore, when cyclic ether is contained in addition to fluoroethylene carbonate, the cyclic ether functions as a so-called binder, fills gaps between the coatings of fluoroethylene carbonate, and strengthens the bonding force between the coatings. The coating thus formed is stable without breaking even in a charge / discharge cycle test at a high temperature, so that the non-aqueous electrolyte does not contact the positive electrode active material or the negative electrode active material, thereby causing an extra reaction. Therefore, it is possible to suppress the capacity reduction during the cycle test.

  If the content of fluoroethylene carbonate is 0.05% by mass or more, the interface between the negative electrode active material layer 24 and the non-aqueous electrolyte of the lithium ion secondary battery 100 or the positive electrode active material layer 14 and the non-aqueous electrolyte A film is formed at the interface, and the discharge capacity can be increased particularly at a low temperature. In addition, when the content of fluoroethylene carbonate is within 4% by mass, an increase in internal impedance of the lithium ion secondary battery 100 can be suppressed, and a sufficient battery capacity can be obtained.

  The content of fluoroethylene carbonate is preferably 0.05 to 2% by mass, and more preferably 0.1 to 1% by mass.

  If the content of the cyclic ether is 0.001% by mass, film formation with fluoroethylene carbonate becomes strong, and as a result, capacity deterioration during charge / discharge cycles at high temperatures can be suppressed. Moreover, if content of cyclic ether is less than 0.5 mass%, effects, such as making the low temperature discharge characteristic which fluoroethylene carbonate has favorable, can be exhibited.

  The content of the cyclic ether is preferably 0.01 to 0.2% by mass, and more preferably 0.01 to 0.1% by mass.

  More preferably, the fluoroethylene carbonate content is 0.05 to 2% by mass and the cyclic ether content is 0.01 to 0.2% by mass. More preferably, the content of fluoroethylene carbonate is 0.1 to 1% by mass and the content of cyclic ether is 0.01 to 0.1% by mass.

  Examples of the cyclic ether include furan, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, and the like. However, since lithium ion conductivity is high at a low temperature and a large discharge capacity is easily obtained, 1,4-dioxane is used. It is preferable that

  In addition, by further adding a sulfur-containing compound, the discharge capacity at low temperatures and the high-temperature cycle characteristics are further improved. As sulfur-containing compounds, sulfolane, ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, glycol sulfate, 1,3-propanediol cyclic sulfate, dimethyl sulfone, diethyl sulfone, ethyl methyl sulfone, divinyl sulfone and Their derivatives are mentioned.

〔式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に水素原子及び炭素数１〜５の炭化水素基からなる群より選ばれる少なくとも一種を表す。〕 Among them, it is preferable that the ethylene glycol sulfate derivative represented by the following formula (1) is contained in an amount of 4% by mass or less because the high-temperature cycle characteristics are particularly good.

[In Formula (1), R < ₁ > and R < ₂ > represents at least 1 type chosen from the group which consists of a hydrogen atom and a C1-C5 hydrocarbon group each independently. ]

  Similarly to the cyclic carbonate having an unsaturated bond, the ethylene glycol sulfate derivative also forms a film on the surface of the negative electrode active material layer 24, and the film also has an effect of suppressing the capacity reduction during the charge / discharge cycle. When an appropriate amount of an ethylene glycol sulfate derivative is added to the cyclic carbonate having an unsaturated bond and the cyclic ether, not only the capacity decrease during the charge / discharge cycle at a higher temperature is suppressed, but also the lithium in the surface coating of the negative electrode active material layer 24 By increasing the ion conductivity, the internal impedance of the lithium ion secondary battery 100 can be reduced, and the discharge capacity at a low temperature can be increased.

  When the content of the ethylene glycol sulfate derivative is within 4 mass%, an increase in internal impedance of the lithium ion secondary battery 100 is suppressed, and a sufficient low-temperature discharge capacity is obtained when the lithium ion secondary battery 100 is manufactured. be able to.

Examples of the ethylene glycol sulfate derivative include ethylene glycol sulfate in which R ₁ and R ₂ are hydrogen atoms, propane 1,2-cyclic sulfate in which one of R ₁ and R ₂ is a hydrogen atom and the other is a methyl group, R ₁ And butane 1,2-cyclic sulfate in which one of R ₂ is a hydrogen atom and the other is an ethyl group, ethylene glycol sulfate is preferable from the viewpoint of improving high-temperature cycle characteristics.

  Moreover, when diallyl carbonate and 2,5-dioxahexanedioic acid dialkyl are contained, the initial discharge capacity tends to increase.

  The non-aqueous solvent preferably contains a cyclic carbonate and a low viscosity solvent. The cyclic carbonate has a dielectric constant of 20 or more so as to promote dissociation of the lithium salt as an electrolyte. A low viscosity solvent refers to an organic solvent having a viscosity of 1.0 cP or less so as to improve the mobility of lithium ions.

  As the cyclic carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and the like can be used. Among them, ethylene carbonate is preferably included. You may mix and use ethylene carbonate with propylene carbonate and butylene carbonate.

  Further, as a low viscosity solvent, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, ethyl propyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, 1,2-dimethoxyethane, 1,2- Diethoxyethane or the like can be used, and it is preferable to include ethyl methyl carbonate from the viewpoint of achieving both a sufficient discharge capacity at a low temperature and good cycle characteristics at a high temperature. Ethyl methyl carbonate may be used by mixing with other low viscosity solvents.

  The ratio of the cyclic carbonate and the low viscosity solvent in the non-aqueous solvent is preferably 1: 9 to 1: 1 by volume.

The electrolytes include LiClO ₄ , LiBF ₄ , LiPF ₆ , LiPOF ₂ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CF ₂ SO ₃ , LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN. (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiN (CF ₃ CF ₂ CO) _{2 and the} like may be mentioned, and two or more kinds may be mixed and used. Good. In particular, it is preferable to include LiPF ₆ that has high conductivity even at a low temperature.

When LiPF ₆ is dissolved in a non-aqueous solvent, the concentration of the electrolyte in the non-aqueous electrolyte is preferably adjusted to 0.5 to 2.0 mol / L. When the concentration of the electrolyte is 0.5 mol / L or more, the conductivity of the nonaqueous electrolytic solution can be sufficiently secured, and a sufficient capacity can be easily obtained during charging and discharging. Moreover, by suppressing the electrolyte concentration to within 2.0 mol / L, it is possible to suppress an increase in the viscosity of the non-aqueous electrolyte, to sufficiently secure the mobility of lithium ions, and to obtain a sufficient capacity during charging and discharging. It becomes easy.

Even when LiPF ₆ is mixed with another electrolyte, the lithium ion concentration in the non-aqueous electrolyte is preferably adjusted to 0.5 to 2.0 mol / L, and the lithium ion concentration from LiPF ₆ is 50 mol%. More preferably, it is contained.

The hydrogen fluoride or fluorine ion produced by reacting LiPF ₆ with moisture, or produced by reacting fluoroethylene carbonate with moisture, is preferably 50 ppm or less in the non-aqueous electrolyte, and 30 ppm or less. Is more preferable. Therefore, the water content in the non-aqueous electrolyte is preferably 50 ppm or less, and more preferably 30 ppm or less.

  The case 50 seals the power generation element 30 and the electrolyte inside. The case 50 is not particularly limited as long as it can suppress leakage of the electrolytic solution to the outside and entry of moisture and the like into the lithium ion secondary battery 100 from the outside. For example, as the case 50, as shown in FIG. 1, a metal laminate film in which a metal foil 52 is coated with a polymer film 54 from both sides can be used. For example, an aluminum foil can be used as the metal foil 52 and a film such as polypropylene can be used as the polymer film 54. For example, the material of the outer polymer film 54 is preferably a polymer having a high melting point such as polyethylene terephthalate (PET) or polyamide, and the material of the inner polymer film 54 is preferably polyethylene or polypropylene.

  The leads 60 and 62 are made of a conductive material such as aluminum or nickel.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples at all.

  By the procedure shown below, the non-aqueous electrolyte for lithium ion secondary batteries and lithium ion secondary batteries of Examples 1 to 48 and Comparative Examples 1 to 9 were prepared and evaluated.

Example 1
First, a negative electrode was produced. In the production of the negative electrode, artificial graphite (90% by mass) as a negative electrode active material, carbon black (2% by mass) as a conductive additive, and polyvinylidene fluoride (hereinafter referred to as PVDF) (8% by mass) as a binder. And dispersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a solvent to obtain a slurry. The obtained slurry was applied to an electrolytic copper foil as a current collector by a doctor blade method and dried at 110 ° C. After drying, rolling was performed to obtain a negative electrode.

Next, a positive electrode was produced. Also in the production of the positive electrode, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (90% by mass) as the positive electrode active material, carbon black (6% by mass) as the conductive additive, and PVDF (4 as the binder) (Mass%) was mixed and dispersed in NMP to obtain a slurry. The obtained slurry was applied to an aluminum foil as a current collector, dried, rolled, and a positive electrode was obtained.

Next, a non-aqueous electrolyte was prepared. LiPF ₆ was added at a rate of 1.0 mol / L to a solution in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3: 7. Furthermore, the non-aqueous electrolyte was obtained by adding 0.05% by mass of fluoroethylene carbonate and 0.01% by mass of 1,4-dioxane to the entire non-aqueous electrolyte.

  A laminated body (element body) was obtained by laminating a separator made of polyethylene between the obtained negative electrode and positive electrode. The obtained laminate is placed in an aluminum laminate pack, a non-aqueous electrolyte is injected into the aluminum laminate pack, and then vacuum-sealed to produce a lithium ion secondary battery (length: 60 mm, width: 85 mm, thickness: 3 mm). did.

(Examples 2-48 and Comparative Examples 1-9)
Same as Example 1 except that the combination of nonaqueous solvent and LiPF ₆ concentration, the content of fluoroethylene carbonate and cyclic ether and ethylene glycol sulfate derivative contained in the nonaqueous electrolyte were changed as shown in Tables 1-3. Thus, lithium ion secondary batteries of Examples 2 to 48 and Comparative Examples 1 to 9 were produced. In Tables 1 to 3, the non-aqueous solvent “EC” is ethylene carbonate, “EMC” is ethyl methyl carbonate, “PC” is propylene carbonate, “DEC” is diethyl carbonate, and “DMC” is dimethyl carbonate. Represents. Further, the content of fluoroethylene carbonate is “FEC content”, the cyclic ether “DOT” is 1,4-dioxane, “THF” is tetrahydrofuran, and “DOL” is 1,3-dioxolane. Further, the ethylene glycol sulfate derivative is referred to as “EGS derivative”, “EGS” represents ethylene glycol sulfate, “PCS” represents propane 1,2-cyclic sulfate, and “BCS” represents butane 1,2-cyclic sulfate.

(Discharge capacity evaluation test)
After the production of the lithium ion secondary battery, the first charge was performed in an environment set at 25 ° C. in a thermostatic bath, and the first discharge was performed immediately after that. The charging was performed at a constant current and constant voltage up to 4.2 V at 30 mA, and the discharging was performed at a constant current of 2.5 mA at 30 mA. The measured value of the discharge capacity (mAh) in the first discharge is shown as the initial discharge capacity (mAh) in Tables 1-3.

(-10 ° C discharge capacity evaluation test)
After the discharge capacity evaluation test, the temperature of the thermostatic chamber containing the battery was set to −10 ° C., and after waiting for 2 hours, charging and discharging were performed at that temperature. The charging was performed at a constant current and constant voltage up to 4.2 V at 30 mA, and the discharging was performed at a constant current of 2.5 mA at 30 mA. In Tables 1 to 3, the discharge capacity at −10 ° C. is shown as “−10 ° C. discharge capacity”.

(45 ° C high-temperature cycle test)
After the discharge capacity evaluation test, the battery was transferred to a thermostat set to 45 ° C., and a charge / discharge cycle test was started. In this cycle test, charging was performed up to 4.2 V in a constant current constant voltage charging mode of 150 mA, and discharging was performed up to 2.5 V in a constant current discharging mode of 150 mA, and this cycle was continuously performed 500 times. The pause time between charging and discharging and between discharging and charging was 10 minutes. Then, after 500 cycles, constant current and constant voltage charging to 4.2 V at 30 mA and constant current discharging to 2.5 V at 30 mA were performed. A value obtained by dividing the discharge capacity at that time by the initial discharge capacity is shown as “capacity after 45 ° C. cycle” in Tables 1 to 3.

(Examples 1 to 6 and Comparative Examples 1 and 2)
First, Table 1 shows the evaluation results when only the content of fluoroethylene carbonate is changed. In addition, the cyclic ether was 1,4-dioxane, and the components shown in Table 1 were fixed and compared except for the content of fluoroethylene carbonate.

  In the initial discharge capacity, it was confirmed that all of the lithium ion secondary batteries of the examples had a sufficient discharge capacity.

  In the discharge capacity at −10 ° C., the comparative example is less than 70 mAh, while the examples in which the content of fluoroethylene carbonate is 0.05 to 4% by mass exceeds 70 mAh. When the content was 0.05 to 2% by mass, it was 80 mAh or more, indicating a good value.

  In the capacity after 45 ° C. cycle, the comparative example is less than 80%, while the examples in which the content of fluoroethylene carbonate is 0.05 to 4% by mass exceeds 80%. When the content of carbonate was 0.1 to 1% by mass, it was 90% or more, indicating an excellent value.

(Examples 4, 7 to 10 and Comparative Examples 3 and 4)
Next, Table 2 shows the evaluation results when the cyclic ether is 1,4-dioxane and the content thereof is changed. In addition, except content of 1, 4- dioxane, it fixed by the structure as shown in Table 2, and compared.

  In the initial discharge capacity, it was confirmed that all the lithium ion secondary batteries of the examples had a sufficient discharge capacity.

  At −10 ° C. discharge capacity, the comparative example is less than 70 mAh, while the examples in which the content of 1,4-dioxane is 0.001 to 0.5% by mass exceeds 70 mAh. When the content of 1,4-dioxane was 0.01 to 0.2% by mass, it was 80 mAh or more, indicating a good value.

  In the capacity after 45 ° C. cycle, the comparative example is less than 80%, while the examples in which the content of 1,4-dioxane is 0.001 to 0.5% by mass exceeds 80%, In particular, when the content of 1,4-dioxane was 0.01 to 0.1% by mass, it was 90% or more, and an excellent value was shown.

(Examples 11 to 48 and Comparative Examples 5 to 9)
The combinations of non-aqueous solvent, LiPF ₆ concentration, and the contents of fluoroethylene carbonate, cyclic ether, and ethylene glycol sulfate derivative contained in the non-aqueous electrolyte were changed as shown in Table 3, and each measurement was performed.

  In the −10 ° C. discharge capacity, all of the comparative examples had a discharge capacity of less than 70 mAh, whereas the fluoroethylene carbonate content was 0.05 to 4 mass% and the cyclic ether content was 0.00. All of the lithium ion secondary batteries having 001 to 0.5% by mass had a discharge capacity exceeding 70 mAh, and particularly showed a good value when the cyclic ether was 1,4-dioxane. In addition, when the content of fluoroethylene carbonate is 0.05 to 2% by mass and the content of cyclic ether is 0.01 to 0.2% by mass, the discharge capacity exceeds 80 mAh and excellent low temperature discharge Showed capacity.

  In the capacity after cycling at 45 ° C., all the comparative examples have a capacity after cycling at 45 ° C. of less than 80%, whereas the content of fluoroethylene carbonate is 0.05 to 4% by mass and the cyclic ether is contained. Any battery having an amount of 0.001 to 0.5% by mass has a capacity of more than 80% after cycling at 45 ° C., in particular, the content of fluoroethylene carbonate is 0.1 to 1% by mass, and the cyclic ether When the content was 0.01 to 0.1% by mass, the capacity after cycling at 45 ° C. exceeded 91%, indicating an excellent value. Furthermore, when the ethylene glycol sulfate derivative was contained, the capacity after cycling at 45 ° C. showed a much larger value than when it was not contained, and in particular, when ethylene glycol sulfate was used, an excellent value was shown.

DESCRIPTION OF SYMBOLS 10 ... Positive electrode, 20 ... Negative electrode, 12 ... Positive electrode collector, 14 ... Positive electrode active material layer, 18 ... Separator, 22 ... Negative electrode collector, 24 ... Negative electrode Active material layer, 30 ... power generation element, 50 ... case, 52 ... metal foil, 54 ... polymer film, 60, 62 ... lead, 100 ... lithium ion secondary battery

Claims (11)

A non-aqueous solvent, an electrolyte,
0.05 to 4% by mass of fluoroethylene carbonate,
0.001 to 0.5 mass% of one or more selected from furan, tetrahydrofuran, 1,3-dioxolane and 1,4-dioxane as the cyclic ether;
A non-aqueous electrolyte for a lithium ion secondary battery, comprising: The non-aqueous electrolyte for a lithium ion secondary battery according to claim 1, wherein the non-aqueous solvent includes ethylene carbonate and ethyl methyl carbonate. The electrolyte for a lithium ion secondary battery nonaqueous electrolytic solution according to any one of claims 1-2, characterized in that it comprises a LiPF _6. Lithium ion secondary batteries for non-aqueous electrolyte according to any one of claims 1 to 3, characterized in that it comprises the following 4 wt% ethylene glycol sulfate derivative represented by the following formula (1).

[In Formula (I), R ₁ and R ₂ each independently represent at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms. ] 5. The non-aqueous electrolyte for a lithium ion secondary battery according to claim 4 , wherein R ₁ and R _{2 of the} ethylene glycol sulfate derivative are both hydrogen atoms. A positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte;
The non-aqueous electrolyte comprises 0.05 to 4% by mass of a non-aqueous solvent, an electrolyte, and fluoroethylene carbonate,
0.001 to 0.5 mass% of one or more selected from furan, tetrahydrofuran, 1,3-dioxolane and 1,4-dioxane as the cyclic ether;
A lithium ion secondary battery comprising: The lithium ion secondary battery according to claim 6, wherein the non-aqueous solvent includes ethylene carbonate and ethyl methyl carbonate. The electrolyte, a lithium ion secondary battery according to any one of claims 6-7, characterized in that it comprises a LiPF _6. The lithium ion secondary battery according to claim 6 , wherein the negative electrode is made of a carbon material. 10. The lithium ion secondary battery according to claim 6 , comprising 4% by mass or less of an ethylene glycol sulfate derivative represented by the following formula (1).

[In Formula (I), R ₁ and R ₂ each independently represent at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms. ] 11. The lithium ion secondary battery according to claim 10 , wherein R ₁ and R ₂ of the ethylene glycol sulfate derivative are both hydrogen atoms.

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