JP6762764B2 - Ion conductive membrane - Google Patents

Description

The present invention relates to an ionic conductive membrane. More specifically, an ion conductive film that can be suitably applied as a battery component of a storage battery (secondary battery) containing a zinc negative electrode, a battery component formed by using the ion conductive film, and the battery component. Concers about batteries configured in use.

Ion conductive membranes that can selectively permeate ions in solution are widely used in various industrial fields. For example, the use of storage batteries is expanding in various fields, including not only the fields of electronic devices such as mobile devices and laptop computers, but also the fields of automobiles and aircraft. Examples of the material used for these storage batteries include a separator, an electrolyte, and a protective film for an electrode arranged between the positive electrode and the negative electrode of the storage battery. For example, an ion conductive film is used as the separator, the electrolyte, and the protective film for the electrode. Can be used.

As the conventional ion conductive membrane, a porous membrane used as a battery separator and the like are disclosed (see, for example, Patent Documents 1 to 3). Further, a separator made of a hydroxide ion conductive inorganic solid electrolyte is disclosed (see, for example, Patent Document 4). Further, a material having anionic conductivity, wherein the anionic conductive material contains an anionic conductivity containing a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. The material is disclosed (see, for example, Patent Document 5).

JP-A-2002-201298 Japanese Unexamined Patent Publication No. 2001-135295 Japanese Unexamined Patent Publication No. 2001-2815 International Publication No. 2013/118561 Japanese Unexamined Patent Publication No. 2015-15229

When zinc is used as the negative electrode active material of the battery, the dendrite formed on the zinc surface during charging short-circuits the positive electrode and the negative electrode, and the battery is killed. Since the porous membranes and the like described in Patent Documents 1 to 3 have through holes, when used as a battery separator, there is room for ingenuity in suppressing the growth of dendrites by the separator and extending the life of the battery. was there. Further, Patent Document 4 discloses a separator made of a hydroxide ion conductive inorganic solid electrolyte. The inorganic solid electrolyte has no flexibility and has a low degree of freedom in morphology. In addition, there was still room for ingenuity in suppressing the growth of dendrites more sufficiently and extending the life of the battery.

The present inventors have used an ion conductive membrane such as an anion conductive membrane for the purpose of sufficiently permeating ions involved in the battery reaction, not impairing the battery performance, and completely suppressing the formation and growth of dendrites. It has been developed and aimed at the practical application of batteries such as storage batteries containing a zinc negative electrode. However, even in the ion conductive membranes (for example, the anionic conductive material described in Patent Document 5) that have been proposed so far, there is room for ingenuity in suppressing the growth of dendrites more sufficiently.

The present invention has been made in view of the above-mentioned current situation, and is an ion conductive film capable of extending the life of a battery by more sufficiently suppressing the growth of dendrites without impairing the battery performance when used as a battery component. The purpose is to provide.

The present inventors aim to more effectively suppress the growth of dendrites and prolong the life of batteries such as storage batteries containing a zinc negative electrode, and are used for battery components such as separators, electrolytes and electrodes. Various ionic conductive membranes were examined. Then, in order for the battery component to more effectively suppress the growth of dendrites, the present inventors make sure that the air permeability value, the puncture strength, and the density with respect to the thickness of the film satisfy a predetermined relationship. We have found that a film that can more effectively suppress the growth of dendrites such as zinc dendrites when used as a battery component can be obtained as a dense and strong film that does not impair battery performance. I came up with the idea that it could be solved. Further, such an ionic conductive film can be used as a separator, an electrolyte, a protective film for electrodes, etc. even in a battery having no problem of dendrite (for example, a primary battery such as a zinc-air battery or an alkali manganese battery). , The additive contained in the electrode that reacts with the counter electrode and induces self-discharge can be prevented from moving to the counter electrode, and the self-discharge can be suppressed. The present inventors have found these advantages and arrived at the present invention.

That is, the present invention has the following formula (1):

(In the formula, T represents the air permeability value (s), F represents the puncture strength (N), ρ represents the density (g / cm ³ ), and L represents the average film thickness (μm). It is an ion conductive film having an X value of 200 or more represented by).
The present invention is also a battery component composed of the ionic conductive membrane of the present invention.
The present invention is further a battery configured using the battery components of the present invention.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Ion conductive membrane>
The ion conductive membrane of the present invention is characterized in that the X value represented by the above formula (1) is 200 or more. The air permeability value represented by T in the above formula is an index showing the ease of passage of gas, and the larger the value, the more difficult it is for gas to pass through. In order to suppress the growth of dendrites, it is the most important factor that there are no through holes through which gas can easily pass. The strength and film thickness of the film are also factors related to the suppression of dendrite growth. The above formula (1) is a relational expression of the air permeability value of the film related to the growth inhibition of these dendrites, the puncture strength and density related to the strength of the film, and the film thickness, and is the most important element among them. It is weighted by squared the value of the air permeability value.
From the viewpoint of more sufficiently suppressing the growth of dendrites, the X value is more preferably 220 or more, further preferably 300 or more, further preferably 500 or more, and preferably 1000 or more. Even more preferably, it is even more preferably 2500 or more, particularly preferably 5000 or more, and most preferably 7000 or more. The X value is, for example, preferably 230000 or less, more preferably 220,000 or less, still more preferably 200,000 or less, but is not particularly limited as long as it allows ions involved in the battery reaction to pass through. It can be said that the upper limit value is infinite, which is particularly preferable in that the effect of the present invention can be more exerted when the same type of film material is used.

The ion conductive membrane of the present invention preferably has an average film thickness L of 5 μm or more, more preferably 30 μm or more, further preferably 50 μm or more, and particularly preferably 80 μm or more. As a result, the performance changes in total, and as a result, the X value becomes larger, the effect of suppressing the growth of dendrites becomes higher, and the battery life can be extended.
The upper limit of the average film thickness L is not particularly limited and can be appropriately set according to the application of the ionic conductive film. However, from the viewpoint of forming a denser film by forming a thin film, and as a thin film, From the viewpoint of increasing the amount of the active material and securing the battery capacity, for example, the average film thickness L is preferably 10,000 μm or less, more preferably 1000 μm or less, and more preferably 500 μm or less. It is more preferably 120 μm or less, and particularly preferably 120 μm or less.
The average film thickness L is the total average thickness of the plurality of layers when the ion conductive film of the present invention has a structure in which a plurality of layers are laminated.
The average film thickness L is measured by the method of Examples described later.

The ion conductive membrane of the present invention preferably has an air permeability value T of 600 s or more, more preferably 800 s or more, further preferably 1100 s or more, still more preferably 4000 s or more. It is even more preferably 5500 s or more, and particularly preferably 8000 s or more.
The upper limit of the air permeability value T is not particularly limited as long as it allows ions involved in the battery reaction to permeate, and is more preferable in that the effects of the present invention can be more exerted when the same type of membrane material is used. It can be said that it is infinite. When the air permeability value T is infinite, the X value is also infinite.
The air permeability value T is measured by the method of Examples described later.

The ion conductive membrane of the present invention preferably has a puncture strength F of 0.1 N or more, more preferably 0.3 N or more, further preferably 0.7 N or more, and 1.5 N or more. It is particularly preferable to have.
The upper limit of the piercing strength F is not particularly limited, but the piercing strength F is preferably 10N or less, more preferably 7N or less, and further preferably 5N or less.
The puncture strength F is measured by the method of Examples described later.

The ion conductive film of the present invention preferably has a density ρ of 0.1 g / cm ³ or more, more preferably 0.3 g / cm ³ or more, and 0.5 g / cm ³ or more. It is more preferably 1.5 g / cm ³ or more, and particularly preferably 1.5 g / cm ³ .
The upper limit of the density ρ is not particularly limited, it is preferred that the density ρ is 10 g / cm ³ or less, more preferably 5 g / cm ³ or less, and more preferably 3 g / cm ³ or less.
The density ρ is measured by the method of Examples described later.

The ion conductive membrane of the present invention has an X value of 200 or more represented by the above formula (1), and is used as a battery component in various batteries by ion conduction to transmit ions involved in the battery reaction. For example, a non-woven fabric; a microporous membrane; a compound containing a polymer and at least one element selected from Groups 1 to 17 of the periodic table (also referred to as an inorganic compound in the present specification). Anionic conductive membranes formed by using an anionic conductive material containing the above; other membranes used as separators described later can be mentioned.
Above all, the ion conductive membrane is preferably a microporous membrane or the anion conductive membrane from the viewpoint of being applied to a battery by anion conduction, and from the viewpoint of extending the life of the battery, the said An anionic conductive membrane is more preferable. In other words, the ionic conductive membrane of the present invention more preferably contains a polymer and a compound containing at least one element selected from Groups 1 to 17 of the Periodic Table. The polymer and the compound will be described later.

The ion conductive membrane of the present invention preferably has a structure in which a plurality of layers are laminated. By adopting a structure in which a plurality of layers are laminated, even if the ion conductive membrane of the present invention has through holes such as a microporous membrane, the positions of the through holes are displaced for each layer, and the through holes are transparent. Since the temper value and the piercing strength are increased, the X value is increased, and the effect of suppressing the growth of dendrite is improved.
The ion conductive membrane of the present invention more preferably has a structure in which three or more layers are laminated, and further preferably has a structure in which four or more layers are laminated.

Hereinafter, the anion conductive membrane will be described.

In the present specification, the anion conductive membrane is a membrane that permeates anions such as hydroxide ions involved in the battery reaction, and is a polymer and at least one selected from Groups 1 to 17 of the periodic table. It contains a compound containing a species element. The anion conductive membrane has the selectivity of an anion that permeates due to the action of an inorganic substance or the like described later. The selectivity of the anion is exhibited even if T in the above formula (1) is increased to infinity so that the gas does not permeate. For example, an anion such as a hydroxide ion easily permeates. big ionic radius be anionic, metal-containing ions derived from the active material (e.g., Zn ^(OH) 4 _2-) transmission, such as is sufficiently prevented. In the present specification, anion conductivity means that an anion having a small ionic radius such as a hydroxide ion is sufficiently permeated, or the permeation performance of the anion. Anions having a large ionic radius, such as metal-containing ions, are more difficult to permeate and may not permeate at all.
Such an anionic conductive film can be suitably applied to a battery component of a battery in which hydroxide ions are involved in a battery reaction (for example, a battery composed of a zinc negative electrode), and can grow dendrites. It can be suppressed to prolong the life of the battery.

The anion conductive film contains a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. In other words, the ionic conductive membrane of the present invention preferably contains a polymer and a compound containing at least one element selected from Groups 1 to 17 of the Periodic Table.

<Compounds containing at least one element selected from Group 1 to Group 17 of the periodic table>
Examples of at least one element selected from Groups 1 to 17 of the periodic table include alkali metals, alkaline earth metals, Mg, Sc, Y, lanthanoids, Ti, Zr, Hf, V, Nb, Ta, and so on. Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, It is preferably at least one element selected from the group consisting of P, Sb, Bi, S, Se, Te, F, Cl, and Br. Among them, at least one element selected from Group 1 to Group 15 of the periodic table is preferable, and Li, Na, K, Cs, Mg, Ca, Ba, Sc, Y, lanthanoid, Ti, Zr, Nb, Cr , Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, Sb, and , At least one element selected from the group consisting of Bi is more preferred. More preferably, Li, Mg, Ca, Ba, Sc, Y, lanthanoids, Ti, Zr, Nb, Cr, Mn, Fe, Ru, Co, Ni, Pd, Cu, Zn, Cd, B, Al, Ga, It is at least one element selected from the group consisting of In and Tl.

Examples of the compound containing at least one element selected from Groups 1 to 17 of the above periodic table include oxides; composite oxides; layered compound hydroxides; hydroxides; clay compounds; solid solutions; Alloys; zeolites; halides; carboxylate compounds; carbonate compounds; hydrogen carbonate compounds; nitrate compounds; sulfuric acid compounds; sulfonic acid compounds; phosphoric acid compounds such as hydroxyapatite; phosphite compounds; hypophosphite compounds, boric acid compounds; Examples thereof include silicic acid compounds; aluminic acid compounds; sulfides; onium compounds; salts and the like. The above compounds are oxides; composite oxides; layered double hydroxides such as hydrotalcite; hydroxides; clay compounds; solid solutions; zeolites; fluorides; phosphoric acid compounds; boric acid compounds; silicic acid compounds; aluminic acid. Compounds; salts are preferred.
Among these, the compound is more preferably at least one compound selected from the group consisting of oxides, hydroxides, layered compound hydroxides, phosphoric acid compounds, and sulfuric acid compounds, and oxides and water. It is more preferably at least one compound selected from the group consisting of oxides, layered compound hydroxides, and sulfuric acid compounds, and particularly preferably layered compound hydroxides and / or oxides. For example, when the compound is a layered double hydroxide, when the anion conductive film is used as a separator, a protective film for electrodes, or the like, an electrolytic solution is taken into the film to improve anion conductivity. Can be done.

The layered double hydroxide has the following formula;
^{_{[M 1 1-x M 2}} x (OH) 2] (A n-) x / n · mH 2 O
(M ¹ represents a divalent metal ion which is any one of Mg, Fe, Zn, Ca, Li, Ni, Co, Cu and Mn. M ² represents Al, Fe, Mn, Co, Cr and In. the ^.A n-representing a trivalent metal ion is any ^{_{one, OH -, Cl -, NO}} 3 -, CO 3 2-, COO - 1 or more valences such as, the .m representing a trivalent following anions 0 The above numbers. N is a number from 1 to 3. x is a number from 0.25 to 0.40). It is preferable that ^An− is a divalent or less anion.
Such layered double hydroxides are naturally occurring (eg, hydrotalcite, manaceite, motukoreaite, stichtite, sjogrenite, barbertite). , Pyroaurite, Iomaite, Chlormagalminite, Hydrocalmite, Green Last 1, Green Last 1, Berthierine, Tacoveite Reevesite), Honesite, Eardlyite, Meixnerite, etc.), or artificially synthesized compounds, which may be dehydrated by firing at 150 ° C to 900 ° C. It may be a compound obtained by decomposing anions in the layers, a compound in which anions in the layers are exchanged with hydroxide ions, or the like. Among these layered double hydroxides, Mg—Al-based layered double hydroxides such as hydrotalcite are preferable. A compound having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a silanol group may be coordinated with the layered double hydroxide.

As the oxide, for example, cerium oxide and zirconium oxide are preferable. More preferably, it is cerium oxide. Further, the cerium oxide may be, for example, one doped with a metal oxide such as samarium oxide, gadolinium oxide or bismuth oxide, or a solid solution with a metal oxide such as zirconium oxide. The oxide may have an oxygen defect.
As the hydroxide, for example, cerium hydroxide and zirconium hydride are preferable.
As the sulfuric acid compound, for example, ettringite is preferable.

As the phosphoric acid compound, for example, hydroxyapatite is preferable.
The above-mentioned hydroxyapatite is a compound typified by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , and is a compound in which the amount of Ca is reduced depending on the conditions at the time of preparation, a hydroxyapatite compound in which an element other than Ca is introduced, and the like. May be used as the above compound.

The compound containing at least one element selected from Groups 1 to 17 of the periodic table preferably has an average particle size of 1000 μm or less. It is more preferably 200 μm or less, further preferably 100 μm or less, particularly preferably 75 μm or less, and most preferably 20 μm or less. On the other hand, the average particle size is preferably 5 nm or more, and more preferably 10 nm or more.
The average particle size is measured by a laser diffraction method according to the method described in Examples.

The shape of the particles of the compound containing at least one element selected from Group 1 to Group 17 of the above periodic table is fine powder, powder, granular, granular, scaly, polyhedral, rod-like, and so on. Examples include curved surface contents. For particles having an average particle size in the above range, for example, a method of crushing the particles with a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle size, and then drying the particles. In addition to the method of selecting the particle size by sieving the coarse particles, the production can be performed by a method of optimizing the preparation conditions at the stage of producing the particles and obtaining (nano) particles having a desired particle size.

Group 1 - compound containing at least one element selected from group 17 of the periodic table, preferably a specific surface area of 0.01 m ² / g or more, more preferably, 0.1 m ² / It is g or more, more preferably 0.5 m ² / g or more. On the other hand, the specific surface area is preferably 500 m ² / g or less.
The specific surface area is measured by a nitrogen adsorption BET method with a specific surface area measuring device.

The ratio of the compound containing at least one element selected from Groups 1 to 17 of the periodic table is preferably 0.1% by mass or more in 100% by mass of the anionic conductive film, and 1% by mass. % Or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. The proportion of the compound is preferably 99.9% by mass or less, more preferably 99% by mass or less, further preferably 90% by mass or less, and further preferably 70% by mass or less. It is preferably 50% by mass or less, and particularly preferably 50% by mass or less.

<Polymer>
Examples of the polymer contained in the anionic conductive film include hydrocarbon site-containing polymers typified by polyolefins such as polyethylene and polypropylene, aromatic group-containing polymers typified by polystyrene and the like; alkylene glycols such as polyethylene oxide and polypropylene oxide. Typical ether group-containing polymers; for polyvinyl alcohol, poly (α-hydroxymethylacrylate), cellulose, methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyalkyl cellulose (for example, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), etc. Representative hydroxyl group-containing polymer; amide bond-containing polymer represented by polyamide, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamide, etc .; imide bond-containing polymer represented by polymaleimide, polyimide, etc.; (meth) acrylic (Meta) acrylic polymer containing a monomer unit derived from an acid alkyl ester monomer as a main component; poly (meth) acrylic acid (salt), polymaleic acid (salt), polyitaconic acid (salt), polymethylene glutal Carboxy group-containing polymers typified by acids (salts), carboxymethyl cellulose, etc. (including carboxy group metal salts (alkali metals, etc.), ammonium salts, etc.); Poly (meth) acrylates, polymaleates, polyitaconsates , A carboxylate-containing polymer typified by polymethylene glutarate, etc .; a halogen atom-containing polymer such as polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene; an epoxy group such as an epoxy resin is bonded by opening a ring. Polymer; sulfonic acid (salt) site-containing polymer; AR ¹ R ² R ³ B (A represents N or P. B represents an anion such as halogen anion or OH ^−. R ¹ , R ² , R ³ Represents the same or different alkyl group having 1 to 7 carbon atoms, hydroxyalkyl group, alkylcarboxyl group, and aromatic ring group. Even if R ¹ , R ² , and R ³ are combined to form a ring structure. A quaternary ammonium salt or a quaternary phosphonium salt-containing polymer represented by a polymer to which a group represented by (good) is bonded; an ion-exchangeable polymer used for a cation / anion exchange film, etc .; a natural rubber. , Rubber-like polymers having unsaturated carbon bonds in the main chain of artificial rubber, etc .; cellulose acetate, chitin, chitosan, alginic acid ( Sugars such as salts); Amino group-containing polymers such as polyethyleneimine; Carbamate group site-containing polymers; Carbamide group site-containing polymers; Epoxide group site-containing polymers; Heterocycles and / or ionized heterocycle sites Containing polymer; polymer alloy; heteroatom-containing polymer; low molecular weight surfactant and the like, and one or more of these can be used.
In addition, these polymers may be crosslinked with a known organic cross-linking agent compound.
Among these, the polymer includes at least one polymer selected from the group consisting of a halogen atom-containing polymer, a rubber-like polymer having an unsaturated carbon bond in the main chain, and a (meth) acrylic polymer. Is preferable. Among them, the polymer may contain at least one polymer selected from the group consisting of a halogen atom-containing polymer, a rubber-like polymer having an unsaturated carbon bond in the main chain, and a (meth) acrylic polymer. More preferred.

<Halogen atom-containing polymer>
The halogen atom-containing polymer is a polymer other than the (meth) acrylic polymer described later or a rubber-like polymer having an unsaturated carbon bond in the main chain and contains a halogen atom. For example, polyvinylidene fluoride. , Fluorine atom-containing polymer such as polytetrafluoroethylene; Chlorine atom-containing polymer such as polyvinyl chloride; Bromine atom-containing polymer; Iodine atom-containing polymer and the like. Among them, the fluorine atom-containing polymer is preferable.

<(Meta) acrylic polymer>
The (meth) acrylic polymer in the present invention contains a monomer unit derived from the (meth) acrylic acid alkyl ester monomer as a main component. The inclusion of a monomer unit derived from a (meth) acrylic acid alkyl ester monomer as a main component is occupied by a monomer unit derived from a (meth) acrylic acid alkyl ester monomer in a (meth) acrylic polymer. It means that the mass ratio is larger than any of the mass ratios of the monomer units derived from each of the other unsaturated monomers described later.
Examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate A (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms such as dodecyl is preferable, and one or more of these can be used.
The (meth) acrylic polymer may be composed of only the (meth) acrylic acid alkyl ester monomer, but the main component is a monomer unit derived from the (meth) acrylic acid alkyl ester monomer. It is preferable that the (meth) acrylic copolymer contains a monomer unit derived from other unsaturated monomers. At that time, from the viewpoint of extending the life of the battery, the mass ratio of the monomer unit derived from the (meth) acrylic acid alkyl ester monomer is 50 mass of the entire monomer unit of the (meth) acrylic polymer. % Or more is preferable. The mass ratio of the monomer unit is more preferably 60% by mass or more, and further preferably 70% by mass or more. The upper limit of the mass ratio of the monomer unit is not particularly limited and is 100% by mass. However, from the viewpoint of improving the mechanical strength of the film, for example, the mass ratio of the monomer unit is 99% by mass or less. Is preferable.

Examples of the other unsaturated monomer include a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester monomer, an oxo group-containing monomer, a nitrogen atom-containing monomer, and a fluorine atom-containing simple substance. Monofunctional monomers such as merits, epoxy group-containing monomers, carbonyl group-containing monomers, aziridinyl group-containing monomers, styrene-based monomers, (meth) acrylic acid aralkyl ester monomers, and polyfunctional Examples include, but the present invention is not limited to such embodiments. These unsaturated monomers may be used alone or in combination of two or more.

Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, and itaconic acid. Examples thereof include carboxy group-containing aliphatic monomers such as monomethyl ester, itaconic acid monobutyl ester, and vinyl benzoic acid, but the present invention is not limited to these examples. These carboxy group-containing monomers may be used alone or in combination of two or more. Among these carboxy group-containing monomers, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid are preferable, and acrylic acid, methacrylic acid and itaconic acid are more preferable from the viewpoint of improving the mechanical strength of the film. preferable. The carboxy group may be in the form of a metal salt of the carboxy group (alkali metal or the like) or a salt such as an ammonium salt.

Examples of the hydroxyl group-containing (meth) acrylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Examples thereof include hydroxyl group-containing (meth) acrylic acid ester monomers having 1 to 18 carbon atoms in ester groups such as 2-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate. It is not limited to illustrations only. These hydroxyl group-containing (meth) acrylic acid ester monomers may be used alone or in combination of two or more.

Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. Meta) acrylate and the like can be mentioned, but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.

Examples of the nitrogen atom-containing monomer include (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-n-propyl (meth). ) Acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropylacrylamide , Acrylamide compounds such as diacetoneacrylamide, nitrogen atom-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, (meth) acrylonitrile and the like. However, the present invention is not limited to such examples. These nitrogen atom-containing monomers may be used alone or in combination of two or more.

Examples of the fluorine atom-containing monomer include a fluorine atom having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Alkyl (meth) acrylate and the like can be mentioned, but the present invention is not limited to such examples. These fluorine atom-containing monomers may be used alone or in combination of two or more.

Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and glycidyl allyl ether. It is not limited to illustrations only. These epoxy group-containing monomers may be used alone or in combination of two or more.

Examples of the carbonyl group-containing monomer include achlorine, formylstyrene, vinyl ethyl ketone, (meth) acrylic oxyalkylpropenal, acetnyl (meth) acrylate, diacetone (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Acetyl acetate, butanediol-1,4-acrylate acetyl acetate, 2- (acetoacetoxy) ethyl (meth) acrylate and the like can be mentioned, but the present invention is not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.

Examples of the aziridinyl group-containing monomer include (meth) acryloyl aziridine, 2-aziridinyl ethyl (meth) acrylate, and the like, but the present invention is not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene and the like, but the present invention is limited to such examples. It's not a thing. These styrene-based monomers may be used alone or in combination of two or more. The styrene-based monomer has an alkyl group such as a methyl group or a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, a functional group such as a halogen atom on the benzene ring. You may. Among the styrene-based monomers, styrene is preferable from the viewpoint of increasing the mechanical strength of the film.

Examples of the (meth) acrylic acid aralkyl ester monomer include benzyl (meth) acrylate, phenylethyl (meth) acrylate, methyl benzyl (meth) acrylate, and naphthylmethyl (meth) acrylate. Examples thereof include (meth) acrylic acid aralkyl ester monomers having 7 to 18 aralkyl groups, but the present invention is not limited to such examples. These (meth) acrylic acid aralkyl ester monomers may be used alone or in combination of two or more.

Among them, suitable monofunctional monomers include, for example, a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester monomer, an oxo group-containing monomer, a fluorine atom-containing monomer, and a nitrogen atom-containing monomer. Examples thereof include a monomer, an epoxy group-containing monomer, a styrene-based monomer, and the like, and these monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, ethylene oxide-modified 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate , Di (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as trimethylolpropylene di (meth) acrylate; Polyethylene glycol di (meth) acrylate having 2 to 50 additional moles of ethylene oxide, additional molar of propylene oxide Alkyldi (meth) acrylates having 2 to 50 molar additions of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di (meth) acrylates having 2 to 50 numbers and tripropylene glycol di (meth) acrylates; ethoxy. Glycerin tri (meth) acrylate, propylene oxide-modified glycerol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylol Tri (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms such as propanetriethoxytri (meth) acrylate; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth). Tetra (meth) acrylate of polyvalent alcohol having 1 to 10 carbon atoms such as acrylate; Pentaerythritol Penta (meth) acrylate, dipentaerythritol (monohydroxy) Penta (meth) acrylate and other polyvalent alcohol having 1 to 10 carbon atoms Penta (meth) acrylate; hexa (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate; bisphenol A di (meth) acrylate, 2- (2'-vinyloxyethoxyethyl). ) (Meta) acrylate, epoxy group-containing (meth) acrylate such as epoxy (meth) acrylate; polyfunctional (meth) acrylate such as urethane (meth) acrylate, etc. However, the present invention is not limited to such an example. Each of these polyfunctional monomers may be used alone, or two or more of them may be used in combination.

The mass ratio of the monomer unit derived from the other unsaturated monomer in the (meth) acrylic polymer is 50% by mass out of 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is preferably less than or equal to, more preferably 40% by mass or less, and further preferably 30% by mass or less. The lower limit of the mass ratio of the monomer unit derived from the other unsaturated monomer is not particularly limited and is 0% by mass, but the mass ratio is preferably 0.1% by mass or more.

When the (meth) acrylic polymer has a monomer unit derived from a carboxy group-containing monomer as a monomer unit derived from another unsaturated monomer, a single amount derived from the carboxy group-containing monomer. The mass ratio of the body unit is preferably 0.5% by mass or more based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer from the viewpoint of extending the life of the manufactured battery. It is more preferably 1% by mass or more, and further preferably 2% by mass or more. Further, the mass ratio of the monomer unit derived from the carboxy group-containing monomer is preferably 8% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably 4% by mass or less.

When the (meth) acrylic polymer has a styrene-based monomer-derived monomer unit as a monomer unit derived from other unsaturated monomers, the styrene-based monomer-derived monomer unit The mass ratio of is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more, based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. Is more preferable. Further, the mass ratio of the monomer unit derived from the styrene-based monomer is preferably 45% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer, which is 35. It is more preferably mass% or less, and further preferably 25 mass% or less.

When the (meth) acrylic polymer has a monomer unit derived from a polyfunctional monomer as a monomer unit derived from another unsaturated monomer, the monomer unit derived from the polyfunctional monomer The mass ratio of is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably 0.5% by mass or more. Further, the mass ratio of the monomer unit derived from the polyfunctional monomer is preferably 5% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably mass% or less.

<Rubber polymer with unsaturated carbon bond in the main chain>
The anion conductive film preferably contains a rubber-like polymer having an unsaturated carbon bond in the main chain. Examples of the rubber-like polymer having an unsaturated carbon bond in the main chain include a conjugated diene polymer.
The conjugated diene polymer is a monomer derived from a monomer having a conjugated diene structure (conjugated diene monomer) such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and chloroprene. It is a polymer having a unit, and examples thereof include natural rubber; artificial rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), and chloroprene rubber (CR). The conjugated diene-based polymer may be a homopolymer or a copolymer, but from the viewpoint of the fact that the inorganic compound can be uniformly present in the anionic conductive film and the mechanical strength of the film. Therefore, it is more preferable that the conjugated diene-based copolymer further has a monomer unit derived from an aromatic vinyl monomer. Further, the composition of the conjugated diene polymer is set as shown below, for example, a monomer unit derived from another unsaturated monomer having a functional group or an acid group or the like is used. The air permeability value, puncture strength, and density of the anionic conductive membrane can be suitably adjusted by including the anion conductive film or preparing it using a known emulsifier.

The conjugated diene-based monomer is preferably an aliphatic conjugated diene-based monomer. As described above, examples of the aliphatic conjugated diene-based monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene and the like, and 1,3-butadiene is preferable. .. The conjugated diene-based monomer may be used alone or in combination of two or more.
In addition, a functional group such as an ester group, a hydroxy group, and a carboxy group may be introduced into the conjugated diene polymer. By introducing these functional groups, the affinity between the conjugated diene polymer and the inorganic compound particles is increased, and the uniformity of the material is improved.

As the conjugated diene polymer, as described above, one or more homopolymers such as polybutadiene and polyisoprene and copolymers can be used. For example, an aromatic vinyl monomer can be used. It is preferably a copolymer further having the derived monomer unit.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and o-. Methylstyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m- Chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene, m-tert-butoxy styrene,
Examples thereof include p-tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene and vinyltoluene. Among these, styrene and α-methylstyrene are preferable because the heat resistance and mechanical strength of the anionic conductive membrane can be increased. These aromatic vinyl monomers may be used alone or in combination of two or more.

In the above conjugated diene polymer, the mass ratio of the monomer unit derived from the aliphatic conjugated diene monomer to the monomer unit derived from the aromatic vinyl monomer is, for example, 1/9 or more, 9 / It is preferably 1 or less, more preferably 2/8 or more and 8/2 or less, and further preferably 3/7 or more and 7/3 or less.

As the conjugated diene polymer, one or more of styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer and the like are preferably used from the viewpoint of film moldability. Can be done. Among these, from the viewpoint of the fact that the inorganic compound can be uniformly present in the anionic conductive film and the mechanical strength of the film, both conjugated diene copolymers such as styrene-butadiene copolymer and acrylonitrile-butadiene copolymer A polymer is more preferable, and a styrene-butadiene copolymer is particularly preferable.
The conjugated diene polymer is a monomer derived from other unsaturated monomers other than the monomer unit derived from the aliphatic conjugated diene monomer and the monomer unit derived from the aromatic vinyl monomer. It may have a unit.

Other unsaturated monomers include acid group-containing vinyl monomers such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide methylpropane sulfonic acid, and styrene sulfonate; (meth). Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (Meta) acrylates such as hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, etc. Alkyl ester monomer; hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; nitrile group-containing vinyl monomer such as (meth) acrylonitrile, (meth) ) (Meta) acrylamide-based monomers such as acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide; divinylbenzene, ethylene glycol dimethacrylate, iso Bifunctional vinyl monomer such as propylene glycol diacrylate and tetramethylene glycol dimethacrylate; containing an alkossisilane group such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxipropyltriethoxysilane A vinyl monomer can be mentioned.

By introducing a highly polar functional group such as an ester group, a hydroxy group, or a carboxy group into the conjugated diene polymer, the affinity between the conjugated diene polymer and the inorganic compound particles is improved, and the inorganic compound particles have an improved affinity. Dispersibility is improved and material uniformity is improved.
The mass ratio of the monomer unit derived from other unsaturated monomers in 100% by mass of the conjugated diene polymer is preferably 40% by mass or less, more preferably 20% by mass or less, and 10% by mass. The following is more preferable, and 5% by mass or less is particularly preferable.
When the monomer unit derived from the (meth) acrylic acid alkyl ester monomer is contained as the monomer unit derived from the other unsaturated monomer, the (meth) acrylic acid alkyl in the conjugated diene polymer is contained. The mass ratio of the monomer unit derived from the ester monomer is smaller than the mass ratio of the monomer unit derived from the conjugated diene-based monomer.

<Other polymers>
When the anionic conductive film contains at least one polymer selected from the group consisting of a halogen atom-containing polymer, a rubber-like polymer having an unsaturated carbon bond in the main chain, and a (meth) acrylic polymer. Other polymers may be included. Other polymers include those mentioned above as polymers contained in the anion conductive film, other than halogen atom-containing polymers, rubber-like polymers having unsaturated carbon bonds in the main chain, and (meth) acrylic polymers. These can be mentioned, and one or more of these can be used. By adding such other polymers, effects such as improving the uniformity of the film and the strength of the film can be obtained.
These polymers may be crosslinked with known organic cross-linking agent compounds.

When a rubber-like polymer having an unsaturated carbon bond in the main chain or a (meth) acrylic polymer is used as the polymer, an anionic conductive film that does not easily allow gas to pass through is formed, and the air permeability value is extremely high. It is thought that it can be increased. As will be described later, when producing an anionic conductive film, a method of kneading a compound containing at least one element selected from Group 1 to Group 17 of the periodic table and a polymer is used. At this time, if the anionic conductive film contains a fluorine atom-containing polymer, a strong force is applied to the fluorine atom-containing polymer during rolling to promote fibrosis of the polymer, and as a result, short-circuiting between electrodes due to dendrite growth occurs. The effect of prevention is higher.

<Polymer preparation method>
The above-mentioned polymer has radical polymerization, radical (alternate) copolymerization, anion polymerization, anion (alternate) copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, etc. Graft (alternate) polymerization, living polymerization, living (alternate) polymerization, dispersion polymerization, emulsification polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, polymerization by light, ultraviolet or electron beam irradiation, metathesis polymerization, electrolytic polymerization It can be obtained by such means. Among these methods, it is preferable to use the emulsion polymerization method from the viewpoint of easy production. When the emulsion polymerization method is used as the polymerization method of the above-mentioned monomer component, the emulsion polymerization may be carried out after mixing the monomer component, the surfactant and the dispersion medium containing water as the main components. The ingredients, surfactants and aqueous medium may be emulsified by stirring to prepare a preemulsion and then emulsion polymerization, or at least one of the monomeric components, surfactants and medium and the rest thereof. Emulsion polymerization may be carried out by mixing with the pre-emulsion of. The monomer component, the surfactant and the medium may be added all at once, may be added in portions, or may be continuously added dropwise.

Examples of the above-mentioned surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like, and one or more of these surfactants are used. be able to.
The anionic surfactant is not particularly limited, and is, for example, an alkyl sulfate salt such as ammonium dodecyl sulfate or sodium dodecyl sulfate; an alkyl sulfonate salt such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, or sodium alkyl diphenyl ether disulfonate; dodecylbenzene sulfone. Alkylaryl sulfonate salts such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfonate, etc .; polyoxyethylene alkylphenyl ether sulfates; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryls Sulfate salt; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate; fatty acid salts such as ammonium laurylate and sodium stearilate; bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, Sulfate ester having an allyl group such as (meth) polyoxyethylene sulfonate salt of acrylate, polyoxyethylene phosphonate salt of (meth) acrylate, sulfonate salt of allyloxymethylalkyloxypolyoxyethylene, or a salt thereof; allyloxymethyl Examples thereof include a sulfate ester salt of alkoxyethylpolyoxyethylene.

The nonionic surfactant is not particularly limited, and is, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid. Examples thereof include monoglyceride, a condensate of ethylene oxide and an aliphatic amine, allyloxymethylalkoxyethyl hydroxypolyoxyethylene, and polyoxyalkylene alkenyl ether. The cationic surfactant is not particularly limited, and examples thereof include an alkylammonium salt such as dodecylammonium chloride. The amphoteric surfactant is not particularly limited, and examples thereof include betaine ester-type surfactants.

The amount of the surfactant used in the above emulsion polymerization method is preferably 0.01% by mass or more from the viewpoint of improving the polymerization stability with respect to 100% by mass of all the monomer components used as the raw material of the polymer. , More preferably 0.1% by mass or more, still more preferably 0.2% by mass or more. Further, from the viewpoint of extending the life of the battery, it is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.

A polymerization initiator can be used for the polymerization of each of the above-mentioned monomer components. As the polymerization initiator, a commonly used one can be used, and is not particularly limited as long as it generates radical molecules by heat. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine], 2,2. Water-soluble azo compounds such as'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid); thermal decomposition initiators such as hydrogen peroxide; hydrogen peroxide and ascorbic acid , T-Butylhydroperoxide and Longarit, Potassium Persulfate and Metal Salt, Ammonium Persulfate and Sodium Hydrogen Persulfate, and other redox-based initiators, and one or more of these can be used. ..

The amount of the polymerization initiator used is preferably 0.02% by mass or more and 2% by mass or less with respect to 100% by mass of the total amount of the monomer components to be subjected to the polymerization reaction. More preferably, it is 0.05% by mass or more and 1% by mass or less.

The temperature of the polymerization reaction for producing the polymer is not particularly limited as long as the polymerization reaction proceeds, but it is preferably carried out at 20 ° C. or higher and 100 ° C. or lower. More preferably, it is 40 ° C. or higher and 90 ° C. or lower. Further, the time of the polymerization reaction is not particularly limited, but in consideration of productivity, 0.5 hours or more and 10 hours or less are preferable. More preferably, it is 1 hour or more and 5 hours or less.

When an emulsion polymerization method using water as a medium is used as the polymerization method of the monomer component, the volume average particle diameter of the polymer obtained as latex particles in the aqueous dispersion is from the viewpoint of forming a uniform film. It is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, and preferably 5000 nm or less from the viewpoint of suppressing permeation of water or ions into the binder (polymer) portion in the membrane. Is 1000 nm or less, more preferably 500 nm or less.
The volume average particle size can be measured using a particle size distribution measuring device according to the method described in Examples.

When these polymers have a functional group, they may have it in the main chain and / or the side chain, and may exist as a binding site with a cross-linking agent. One type of these polymers may be used, or two or more types may be used.
The polymer may be an ester bond, an amide bond, an ionic bond, a van der Waals bond, an agostic interaction, a hydrogen bond, an acetal bond, a ketal bond, an ether bond, or the like, depending on the layered compound aqueous compound or other organic cross-linking agent compound. Cross-linking via peroxide bond, carbon-carbon bond, carbon-nitrogen bond, carbon-oxygen bond, carbon-sulfur bond, carbamate bond, thiocarbamate bond, carbamide bond, thiocarbamide bond, oxazoline site-containing bond, triazine bond, etc. It may have been done.

The weight average molecular weight of the polymer is preferably 200 to 7000000. Thereby, the anion conductivity, flexibility and the like of the anion conductive film can be adjusted. The weight average molecular weight is more preferably 400 to 6500000, and even more preferably 500 to 500000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent weight average molecular weight.
Equipment: HCL-8220GPC manufactured by Tosoh Corporation
Column: TSKgel Super AWM-H
Eluent (LiBr · H ₂ O, NMP containing phosphoric acid): 0.01 mol / L
The above range description of "200 to 7000000" means a range including the numerical values of the upper end and the lower end of the range. That is, "200 to 7000000" has the same meaning as "200 or more and 7000000 or less".
All the range descriptions using "~" described in the present invention mean the range including the numerical values of the upper end and the lower end of the range in the same manner.

From the viewpoint of the strength and ionic conductivity of the anionic conductive membrane, the mass ratio of the polymer is preferably 0.1% by mass or more, and preferably 1% by mass or more, based on 100% by mass of the anionic conductive membrane. More preferably, it is more preferably 10% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The mass ratio of the polymer is preferably 99.9% by mass or less, more preferably 99% by mass or less, further preferably 90% by mass or less, and 80% by mass or less. Is more preferable, and 70% by mass or less is particularly preferable.
Here, the preferable mass ratio of the polymer in the anionic conductive membrane is described, but the preferable mass ratio of the polymer in the anionic conductive membrane-forming material for forming the anionic conductive membrane is also the same.
The above mass ratio is the total of the mass ratios of two or more kinds of polymers when there are two or more kinds of polymers.

The mass ratio of the polymer to the compound containing at least one element selected from Groups 1 to 17 of the periodic table in the anion conductive film is preferably 5000000/1 to 1/10000. It is more preferably 2000000/1 to 1/10000, and even more preferably 1000000/1 to 1/10000.

<Other ingredients>
The anion conductive film may further contain other components as long as it contains a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. Further, the other components may be one kind or two or more kinds.

The other components are not particularly limited, and examples thereof include zinc-containing compounds, alumina, silica, conductive carbon, and conductive ceramics. Other components can function to assist anion conductivity.

<Manufacturing method of anionic conductive membrane>
When producing the anionic conductive film, a method including a step of kneading and rolling the anionic conductive material can be used. Anionic conductive materials are materials used to form anionic conductive membranes and are required together with polymers and compounds containing at least one element selected from Groups 1 to 17 of the Periodic Table. Correspondingly, it refers to those containing the above other components.

The anion conductive film is preferably obtained through a step of kneading the anion conductive material.
For example, the above-mentioned other components are kneaded together with a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table, if necessary. For kneading, a mixer, a blender, a kneader, a bead mill, a ready mill, a ball mill or the like can be used. At the time of kneading, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran or N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be added. In the above kneading, it is preferable to obtain a dispersion in which the polymer is dispersed in water or the like. As a result, the obtained anionic conductive film becomes more dense, and the air permeability value and the puncture strength become larger, so that the X value becomes larger. This makes it more effective in blocking the growth of dendrites.

The kneading time can be set as appropriate, but is preferably 2 minutes or longer, more preferably 4 minutes or longer, further preferably 6 minutes or longer, and particularly preferably 8 minutes or longer. In particular, it is preferable that the kneading time is long under high temperature conditions (for example, 40 ° C. or higher). As a result, the obtained anionic conductive film becomes more dense, and the air permeability value and the puncture strength become larger, so that the X value becomes larger.
The upper limit of the kneading time is not particularly limited, but for example, the kneading time is preferably 30 minutes or less.

The kneading temperature can be appropriately set, but is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. As a result, the obtained anionic conductive film becomes more dense, and the air permeability value and the puncture strength become larger, so that the X value becomes larger.
The upper limit of the kneading temperature is not particularly limited as long as the polymer and the compound containing at least one element selected from Group 1 to Group 17 of the periodic table are not decomposed. For example, the kneading temperature is set to 200 ° C. or lower. It is preferable to do so.

It is preferable that the anion conductive film is obtained by undergoing a step of kneading the anion conductive material and then a step of further rolling.
When the anionic conductive film is used as a protective film for an electrode, the anionic conductive material may be rolled on the active material layer of the electrode.
When the anion conductive material contains a fluorine atom-containing polymer, a strong force is applied to the fluorine atom-containing polymer during rolling to promote fibrosis of the polymer, and as a result, the air permeability value and strength of the anion conductive film are obtained. Therefore, the X value becomes larger.

The ion conductive film of the present invention represented by the above anionic conductive film does not impair battery performance and can more sufficiently suppress the growth of dendrite. Therefore, a battery separator, an electrolyte (film), a protective film for electrodes, etc. A secondary battery (for example, a manganese / zinc (storage) battery, a nickel / hydrogen (storage) battery, a nickel / zinc (storage)), which is composed of a negative electrode having a high energy density and is safe and inexpensive. Batteries, zinc ion (storage) batteries, silver / zinc (storage) batteries, zinc / halogen (storage) batteries, etc.) can be extended in life, and there is a possibility that they can be widely used. Further, such an ionic conductive film includes an alkaline (ion) (storage) battery, an alkaline earth (ion) (storage) battery, a nickel / hydrogen (storage) battery, a nickel / cadmium (storage) battery, and a lead storage battery. It can also be used for electrochemical devices such as fuel cells and capacitors, as components of primary batteries such as air zinc batteries and alkaline manganese batteries, ion exchange materials, trace element adsorbents, and the like.

<Battery components>
The present invention is also a battery component composed of the ionic conductive membrane of the present invention. Examples of the battery component include a separator, an electrolyte, an electrode and the like.

When the battery component of the present invention is an electrode, the ion conductive film of the present invention is used as a protective film for an electrode that covers the active material layer of the electrode.

The electrode contains an active material and a binder in the active material layer, and may further contain a conductive auxiliary agent, other components, and the like.

The active material may be a positive electrode active material or a negative electrode active material.
When the electrode of the present invention is a negative electrode, the active material of the negative electrode is carbon type, cadmium type, lithium type, sodium type, magnesium type, lead type, zinc type, tin type, silicon-containing material, hydrogen storage alloy. A material usually used as a negative electrode active material of a battery, such as a material or a noble metal material such as platinum, can be used. Among these, the active material in the electrode of the present invention preferably contains zinc type or cadmium type, and more preferably contains zinc type. As a result, the effect of the present invention becomes remarkable. For example, the zinc species means a simple substance of zinc or a zinc compound, and the cadmium species means a simple substance of cadmium or a cadmium compound. The same applies to lithium type, sodium type, magnesium type, lead type, zinc type, and tin type.

When the electrode of the present invention is a positive electrode, as the active material of the positive electrode, a material usually used as a positive electrode active material of a primary battery or a secondary battery can be used. For example, nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, and cobalt-containing nickel hydroxide; manganese-containing compounds such as manganese dioxide; silver oxide; lithium-containing compounds such as lithium cobaltate; iron-containing compounds; and other cobalt-containing compounds. Examples include compounds.
The active material contained in the active material layer of the electrode of the present invention is preferably the active material of the negative electrode.

Various known polymers can be used as the binder, but either thermoplastic or thermosetting may be used, and halogen atom-containing polymers such as polyvinylidene fluoride and polytetrafluoroethylene, polyolefins and the like can be used. Carboxide site-containing polymer, aromatic group-containing polymer such as polystyrene; ether group-containing polymer such as alkylene glycol; hydroxyl group-containing polymer such as polyvinyl alcohol; amide bond-containing polymer such as polyamide and polyacrylamide; imide group-containing polymer such as polymaleimide Polymers; carboxyl group-containing polymers such as poly (meth) acrylic acid; carboxylic acid base-containing polymers such as poly (meth) acrylate; sulfonate site-containing polymers; quaternary ammonium salts and quaternary phosphonium salt-containing polymers Ion-exchangeable polymers; Natural rubber; Artificial rubber such as styrene butadiene rubber (SBR); Sugars such as hydroxyalkyl cellulose (for example, hydroxyethyl cellulose), carboxymethyl cellulose; Amino group-containing polymers such as polyethylene imine; Polyurethane and the like. Be done. The binder may be used alone or in combination of two or more.

The conductive auxiliary agent is not particularly limited, and is, for example, one or more of conductive carbon, conductive ceramics, metals such as zinc, copper, brass, nickel, silver, bismuth, indium, lead, and tin. Can be used.

As the other component, one or more of a compound having at least one element selected from the group consisting of elements belonging to Group 1 to Group 17 of the periodic table, an organic compound, and an organic compound salt is used. be able to.

The average thickness of the active material layer according to the present invention is preferably 100 μm or more, more preferably 200 μm or more, further preferably 500 μm or more, and the ion conductive film of the present invention is a protective film for electrodes. When used as a battery, it is particularly preferably 1 mm or more from the viewpoint of suppressing the dropping of the active material and forming a battery having a high energy density on which a large amount of the active material is mounted. The average thickness of the active material layer is, for example, preferably 10 mm or less, and preferably 5 mm or less.
The average thickness of the active material layer can be calculated by arbitrarily measuring 5 points with a micrometer.

The electrodes of the present invention further include a current collector.
The current collector includes (electrolytic) copper foil, copper mesh (expanded metal), foamed copper, punching copper, copper alloys such as brass, brass foil, brass mesh (expanded metal), foamed brass, punching brass, nickel foil. , Corrosion resistant nickel, nickel mesh (expanded metal), punching nickel, metallic zinc, corrosion resistant metallic zinc, zinc foil, zinc mesh (expanded metal), (punching) steel plate, non-woven fabric with conductivity; Ni, Zn, Sn, Pb・ (Electrolytic) copper foil with Hg, Bi, In, Tl, brass, etc. added ・ Copper mesh (expanded metal) ・ Copper foam ・ Punching copper ・ Copper alloy such as brass ・ Brass foil ・ Brass mesh (expanded metal) ・ Foam Brass, punching brass, nickel foil, corrosion-resistant nickel, nickel mesh (expanded metal), punching nickel, metallic zinc, corrosion-resistant metal zinc, zinc foil, zinc mesh (expanded metal), (punching) steel plate, non-woven fabric; Ni, Zn, Sn・ (Electrolytic) copper foil plated with Pb, Hg, Bi, In, Tl, brass, etc. ・ Copper mesh (expanded metal) ・ Copper foam ・ Punching copper ・ Copper alloy such as brass ・ Brass foil ・ Brass mesh (expanded metal) ) ・ Foamed brass ・ Punching brass ・ Nickel foil ・ Corrosion resistant nickel ・ Nickel mesh (expanded metal) ・ Punching nickel ・ Metallic zinc ・ Corrosion resistant metal zinc ・ Zinc foil ・ Zinc mesh (expanded metal) ・ (Punching) steel plate ・ Non-woven fabric; Silver; Examples include materials used as current collectors and containers for alkaline (storage) batteries and air-zinc batteries.

When the battery component of the present invention is an electrolyte, the ion conductive membrane of the present invention can be used as a solid electrolyte.
When the battery component of the present invention is a separator, the ion conductive film of the present invention can be used as the separator.

<Battery configured by using the battery component of the present invention>
The present invention is also a battery configured using the battery components of the present invention.
The battery of the present invention may include any of a separator, a positive electrode, a negative electrode, and an electrolytic solution (electrolyte) including the ion conductive film of the present invention.
As the positive electrode and negative electrode active material layers and current collectors included in the battery of the present invention, the above-mentioned ones can be used.

As described above, the negative electrode used in the battery of the present invention preferably uses zinc type or cadmium type as an active material, and more preferably zinc type as an active material. Therefore, it is one of the preferred embodiments of the present invention that the battery of the present invention is a battery containing the electrode of the present invention as a zinc negative electrode using zinc type or cadmium type (more preferably zinc type) as an active material. It is one.
Further, as the form of the battery including the zinc negative electrode of the present invention, a primary battery, a rechargeable secondary battery, a mechanical culture (mechanical replacement of the zinc negative electrode), and a third electrode are used. Any form may be used, such as (an electrode suitable for charging and an electrode suitable for discharging are used as the positive electrode, respectively).

As the electrolytic solution used for the battery of the present invention, a solution usually used as an electrolytic solution for a storage battery can be used except when a solid electrolyte composed of the ion conductive film of the present invention is used, and is not particularly limited. , Ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyl tetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, benzonitrile, ionic liquid, Fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like can be mentioned. The organic solvent-based electrolytic solution can be used alone or in combination of two or more. Examples of the aqueous electrolytic solution include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, zinc acetate aqueous solution and the like. Among these, alkaline electrolytes such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, and lithium hydroxide aqueous solution are preferable. The above-mentioned aqueous electrolytic solution can be used alone or in combination of two or more. The water-based electrolytic solution may contain the above-mentioned organic solvent-based electrolytic solution.

In the battery of the present invention, when the ion conductive film of the present invention is used for a battery component (electrolyte and / or electrode) other than the separator, the ion conductive film acts as a separator, and therefore a separate separator is used. You don't have to. In addition, one or more commonly used separators may be used. The separator may be any member as long as it is a member that separates the positive electrode and the negative electrode, holds the electrolytic solution, and secures ionic conductivity between the positive electrode and the negative electrode. Arocyclic site-containing polymers such as polytetrafluoroethylene site-containing polymer, polyvinylidene fluoride site-containing polymer, cellulose, fibrillated cellulose, biscorayon, cellulose acetate, hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol-containing polymer, cellophane, and polystyrene. , Polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, polyhalogenated vinyl site-containing polymer, polyamide site-containing polymer, polyimide site-containing polymer, ester site-containing polymer such as nylon, poly (meth) acrylic acid site-containing polymer, poly (Meta) acrylate site-containing polymer, hydroxyl group-containing polymer such as polyisoprenol or poly (meth) allyl alcohol, carbonate group-containing polymer such as polycarbonate, ester group-containing polymer such as polyester, carbamate or carbamide group site such as polyurethane Containing polymer, agar, gel compound, organic-inorganic hybrid (composite) compound, ion-exchange film polymer, cyclized polymer, sulfonate-containing polymer, quaternary ammonium salt-containing polymer, quaternary phosphonium salt polymer, cyclic hydrocarbon Examples thereof include group-containing polymers, ether group-containing polymers, and inorganic substances such as ceramics. When a separator is used, the separator may be one of these or two or more.
The laminated structure in which the ion conductive film of the present invention and another separator are laminated may be an integrated laminated structure or a laminated structure in which they are independently laminated. When the films are in close contact with each other, the laminated structure may have a clear interface, or may form a laminated structure having a mixed layer in which these components are mixed.

The battery of the present invention can be produced by appropriately using a known method. For example, a battery can be manufactured by arranging a negative electrode in a battery cell, introducing an electrolyte solution into the battery cell, and further arranging a positive electrode, a reference electrode, a separator, and the like as necessary.

The ion conductive film of the present invention has the above-mentioned structure, and when used as a battery component, it does not impair the battery performance, can sufficiently suppress the growth of dendrites, and prolong the life of the battery. Can be done.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".

Various measurements in the examples were carried out by the following methods.
<Measurement of air permeability value>
In the embodiment, the air permeability value T (s) is measured by the Oken type air permeability smoothness measuring device KY-55 (manufactured by Asahi Seiko Co., Ltd.) according to the JIS P8117 (2009) Oken type testing machine method. It was measured and the average value of the measured values was calculated. Further, the upper limit of the measurement time was set to 30,000 s, and when the upper limit value of the measurement was exceeded, the air permeability value was set to 30,000 s. That is, in the embodiment, the air permeability value of 30,000 s means that the air permeability value is at least 30,000 s, and the X value obtained from this is the value of the X value when it is estimated to be the least.

<Measurement of puncture strength>
The puncture strength F (N) was measured with a digital force gauge ZTA-50N (manufactured by Imada) according to JIS Z1707 (1997). The test piece was fixed, and a semicircular needle-shaped jig with a diameter of 1.0 mm and a tip shape radius of 0.5 mm was pierced at a speed of 50 ± 5 mm per minute, and the maximum stress until the tip of the jig penetrated was measured. .. The number of test pieces was 5 or more, and the average value was calculated.

<Density measurement>
The density ρ (g / cm ³ ) was calculated by measuring the mass and volume of the test piece of the ionic conductive membrane and dividing the mass by the volume. The volume of the test piece was calculated by measuring the length in the vertical direction and the length in the horizontal direction of the test piece using a caliper, and measuring the film thickness based on the following film thickness measuring method. The mass of the test piece was measured using a precision balance having four decimal places for the test piece whose volume was measured.

<Measurement of film thickness>
The average film thickness L (μm) was calculated as an average value of 5 points arbitrarily measured using a Digimatic Indicator 543-394 manufactured by Mitutoyo Co., Ltd.

<Calculation of X value>
The X value is the following formula (1) using the air permeability value T (s), the puncture strength F (N), the density ρ (g / cm ³ ), and the film thickness L (μm) calculated by the above measurement method. Obtained by.

<Average particle size of inorganic compound particles>
The average particle size of the inorganic compound particles was measured by a laser diffraction method using a dispersion in which the inorganic compound particles were dispersed in the following dispersion medium (device name: laser diffraction / scattering type particle size distribution measuring device manufactured by HORIBA). LA-950, dispersion medium: ion-exchanged water containing 0.2% by mass sodium hexametaphosphate).
<Volume average particle size of polymer aqueous dispersion>
The volume average particle size of the polymer aqueous dispersion is obtained by diluting the aqueous dispersion of the polymer with distilled water, collecting about 10 mL of the obtained diluent in a glass cell, and using this as a particle size distribution measuring instrument by a dynamic light scattering method. Measurement was performed using a product name: NICOMP Model 380, manufactured by Particle Sizing Systems, Inc.

<Glass transition temperature>
The glass transition temperature of the polymer is such that the polymer is applied to a glass plate and dried at 120 ° C. for 1 hour to form a polymer film, and the obtained polymer film is subjected to a differential scanning calorimeter (device name: thermal analyzer DSC3100S). , BRVKER).

<Liquid absorption rate>
On specimens 10 sheets cut from any location 25 mm × 25 mm square of the anion conducting membrane, the mass of each dry _{(M b)} and, KOH aqueous solution 6.7 mol / L concentration saturated with zinc oxide was liquid absorption rate by respectively calculated from the mass when immersed overnight (M _a), obtain their average values as two significant figures on.

<Swelling degree>
Ten test pieces cut into 25 mm × 25 mm squares from any location of the anionic conductive membrane were immersed overnight in a dry film thickness (T _b ) and a 6.7 mol / L concentration KOH aqueous solution. respectively calculated from the thickness (T _a) of the time was, and swelling degree by obtaining an average value as two significant figures.

<Resistance value>
The resistance value (Ω) was measured under the following conditions.
・ Number of charged cells: 5 cells (state the average value)
-Cell composition Working electrode: Ni plate counter electrode: Ni plate Electrolyte: 6.7 mol / L concentration KOH aqueous solution saturated with zinc oxide Measurement sample: Immerse in the above electrolyte overnight Effective area: φ15 mm
・ Measure AC impedance. After allowing to stand in a constant temperature bath at 25 ° C. for 30 minutes, the measurement was carried out under the following conditions.
Applied voltage: 10 mV vs. Open circuit voltage frequency range: 100kHz to 100Hz
The resistance value (R) was calculated from the intercept component (Ra) obtained by impedance and the intercept component (Rb) when the measurement sample was not included by the following formula.
R = (Ra-Rb)

<Area ratio of compound particles to anionic conductive film-forming material components other than compounds>
The area ratio is the membrane cross section obtained by cutting the anionic conductive membrane perpendicular to the surface of the membrane (the membrane cross section was prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). Using a scanning electron microscope, 10,000-fold magnified photographs were taken at five locations at arbitrary locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film forming material portion was further extracted, and the material portion was converted into a black and white display. In such an image, the portion other than the inorganic compound particles is displayed in black, and the portion of the inorganic compound particles is displayed in white. Using image analysis software manufactured by Image matrix Co., Ltd., the ratio of the total area of the inorganic compound particle portion to the total area of the portion other than the inorganic compound particle in the obtained image was determined. At the time of treatment, the contrast between the black part and the white part was clarified so that the particles could be clearly separated.

<Ratio of voids>
Similar to the above area ratio, the membrane cross section obtained by cutting the anionic conductive membrane perpendicularly to the surface of the membrane (the membrane cross section is prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). With a scanning electron microscope, 10,000-fold magnified photographs were taken at five locations at arbitrary locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film forming material portion was further extracted, and the material portion was converted into a black and white display. In such an image, the void portion is displayed in black, and the other component portions are displayed in white. The ratio of the void portion to the image was determined by using image analysis software manufactured by Image metrology for the obtained image. At the time of treatment, the contrast between the black portion and the white portion was clarified so that the void portion could be clearly separated.

<Cross-sectional particle size of inorganic compound particles in the membrane>
Similar to the above area ratio, the membrane cross section obtained by cutting the anionic conductive membrane perpendicularly to the surface of the membrane (the membrane cross section is prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). A scanning electron microscope was used to take 10,000-fold magnified photographs of any five locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. At this time, the contrast was adjusted and stored so that only the inorganic compound particle portion could be displayed in white by the following image processing. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film forming material portion was further extracted, and the material portion was converted into a black and white display. In the image, the inorganic compound particle portion was displayed in white, and the size of the white portion in the image was determined as the particle diameter of the inorganic compound particle using image analysis software manufactured by Image matrix Co., Ltd. for the obtained image. At the time of treatment, the contrast between the black part and the white part was clarified so that the particles could be clearly separated. The measurement was performed on 100 particles, and the average value was taken as the cross-sectional particle diameter. When the observed particles are elliptical particles, 100 particles are measured on each of the major axis side and the minor axis side, and the average value of the respective average values is the cross-sectional particle diameter of the particles in the film. And said.

<Preparation example of (meth) acrylic polymer>
[Preparation Example 1]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 26 parts by mass of deionized water, 4 parts by mass of 10% sodium dodecylbenzene sulfonate aqueous solution, 1.5 parts by mass of 1,6-hexanediol dimethacrylate, 46.5 parts by mass of methyl methacrylate, and methacrylic acid were added to the dropping funnel. A pre-emulsion consisting of 50 parts by mass of dodecyl and 2 parts by mass of acrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.2% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 190 nm was obtained at 7.8.

[Preparation Example 2]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, a preemulsion consisting of 26 parts by mass of deionized water, 4 parts by mass of a 10% sodium dodecylbenzene sulfonate aqueous solution, 54 parts by mass of methyl methacrylate, 44 parts by mass of dodecyl methacrylate, and 2 parts by mass of acrylic acid was prepared in the dropping funnel. did. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 47.8% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 7.6 nm was obtained.

(Example 1)
A microporous structure composed of a zinc negative electrode prepared by pasting an active material obtained by kneading zinc oxide and polytetrafluoroethylene (PTFE) in a mass ratio of 96: 4 onto punching nickel, and a polyolefin having an average pore size of 100 nm as a separator. An ionic conductive film formed by stacking four films (average thickness 25 μm) was arranged, and a battery cell using a nickel positive electrode as a counter electrode and an Ag / AgO electrode as a reference electrode was constructed. A current with a current density of 30 mA / cm ² was passed between the counter electrode and the negative electrode, and a charge / discharge test was performed with an electric capacity of 25% of the negative electrode capacity. As a result, a life of 300 cycles was observed.

(Example 2)
Hydrotalcite as an inorganic compound and PTFE dispersion (trade name: Polyflon D-210, manufactured by Daikin Industries, Ltd.) as a polymer are used in a mass ratio of 4: 6 and kneaded at 30 ° C. for 3 minutes to achieve an average film thickness. A 100 μm ion conductive film was prepared.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the above ion conductive membrane as a separator, a life of 300 cycles was observed.

(Example 3)
When constructing the ion conductive membrane of Example 2, the hydrotalcite and the dispersion of PTFE were kneaded at 30 ° C. for 5 minutes to prepare an ion conductive membrane having an average film thickness of 300 μm.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the above ion conductive membrane as a separator, a life of 400 cycles was observed.

(Example 4)
When constructing the ion conductive membrane of Example 2, the hydrotalcite and the dispersion of PTFE were kneaded at 50 ° C. for 5 minutes to prepare an ion conductive membrane having an average film thickness of 300 μm.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the above ion conductive membrane as a separator, a life of 450 cycles was observed.

(Example 5)
When constructing the ion conductive membrane of Example 2, the hydrotalcite and the dispersion of PTFE were kneaded at 50 ° C. for 10 minutes to prepare an ion conductive membrane having an average film thickness of 300 μm.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the above ion conductive membrane as a separator, a life of 500 cycles was observed.

(Example 6)
When constructing the ion conductive membrane of Example 2, the hydrotalcite and the dispersion of PTFE were kneaded at 50 ° C. for 10 minutes, and further rolled to prepare an ion conductive membrane having an average film thickness of 100 μm. did. When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the above ion conductive membrane as a separator, a life of 500 cycles was observed.

(Example 7)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 100 parts by mass, aqueous dispersion of styrene-butadiene copolymer (product name: TRD-2001, manufactured by JSR) , Solid content 48%) 100 parts by mass, PTFE aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) 5 parts by mass and carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel Finechem) 3 mass Weigh parts and 15 parts by mass of pure water, knead with a kneader until uniform, and then roll press the obtained kneaded product to a thickness of 100 μm to form an ionic conductive film. Obtained.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the ion conductive membrane obtained as a separator, a life of 420 cycles was observed.

(Example 8)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 100 parts by mass, 100 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 1, carboxy Weigh 3 parts by mass of methyl cellulose (trade name: Daicel 1380, manufactured by Daicel Fine Chem Ltd.) and 10 parts by mass of pure water, knead with a kneader until uniform, and then use the obtained kneaded product. An ion conductive film was obtained by roll pressing until the thickness reached 100 μm and further heat-treating at 120 ° C. for 10 minutes.
When a charge / discharge test was performed in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the ion conductive membrane obtained as a separator was used, a life of 490 cycles was observed.

(Example 9)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 2. To obtain an ionic conductive film.
When a charge / discharge test was carried out in the same manner as in Example 1 using the same negative electrode and positive electrode as in Example 1 and the ion conductive membrane obtained as a separator, a life of 520 cycles was observed.

(Example 10)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 100 parts by mass, aqueous dispersion of acrylonitrile-butadiene copolymer (product name: NA-13, Nippon A & L Co., Ltd.) Made by, solid content 47%) 100 parts by mass, PTFE aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) 5 parts by mass and carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel Finechem) 3 Weigh parts by mass and 15 parts by mass of pure water, knead them with a kneader until they become uniform, and then roll press the obtained kneaded product to a thickness of 100 μm to form an ionic conductive film. Got
When the same negative electrode and positive electrode as in Example 1 were used and the ion conductive membrane obtained as a separator was used, a lifetime of 440 cycles was observed.

(Example 11)
In Example 7, 100 parts by mass of the aqueous dispersion of the styrene-butadiene copolymer was changed to 35 parts by mass, and 15 parts by mass of pure water was changed to 28 parts by mass in the same manner as in Example 7. As a result of preparing an ionic conductive film and performing a charge / discharge test, a lifetime of 370 cycles was observed.
Here, the liquid absorption rate of the obtained anionic conductive film was 10%, and the swelling degree was 0.6%.
The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the anionic conductive membrane portion of the obtained anionic conductive membrane is 69/31, which is the area of voids with respect to the entire cross section of the membrane. The ratio was 4.8%. The cross-sectional particle diameter of the hydrotalcite particles in the anionic conductive film at this time was 0.39 μm.
Further, the resistance value (R) of the obtained anionic conductive film was 0.19Ω.

(Example 12)
100 parts by mass of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm), 80 parts by mass of the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1, and 15 parts by mass of pure water was weighed and kneaded using a kneader until a uniform state was obtained, and then the obtained kneaded product was roll-pressed at a roll interval of 100 μm to obtain an ion conductive film.
When the same negative electrode and positive electrode as in Example 1 were used and the charge / discharge test was performed in the same manner as in Example 1 using the ion conductive membrane obtained as a separator, a life of 380 cycles was observed.
Here, the liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 1.5%.
The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the anionic conductive membrane portion of the obtained anionic conductive membrane is 59/41, which is the area of voids with respect to the entire cross section of the membrane. The ratio was 5.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anionic conductive film at this time was 0.43 μm.
The resistance value (R) of the obtained anionic conductive membrane was 0.20Ω.

(Comparative Example 1)
A zinc negative electrode prepared by pasting an active material obtained by kneading zinc oxide and PTFE in a mass ratio of 96: 4 on punching nickel and a non-woven fabric (average film thickness: 1000 μm) as a separator are arranged, and a nickel positive electrode is used as a counter electrode. A battery cell using an Ag / AgO electrode as a pole was constructed. A current with a current density of 30 mA / cm ² was passed between the counter electrode and the negative electrode, and a charge / discharge test was performed with an electric capacity of 25% of the negative electrode capacity. As a result, the positive electrode and the negative electrode were short-circuited in 5 cycles.

(Comparative Example 2)
Using the same negative electrode and positive electrode as in Comparative Example 1, an ionic conductive film formed of one microporous film (average film thickness: 25 μm) composed of polyolefin having an average pore diameter of 100 nm was arranged as a separator, and the same. When the charge / discharge test was attempted, a short circuit occurred in 100 cycles.

(Comparative Example 3)
Hydrotalcite as an inorganic compound and PTFE dispersion (trade name: Polyflon D-210, manufactured by Daikin Industries, Ltd.) as a polymer are used in a mass ratio of 4: 6, kneaded at 30 ° C. for 3 minutes, and ion conduction of 50 μm. A sex membrane was created. When the same negative electrode and positive electrode as in Comparative Example 1 were used and the above-mentioned ion conductive membrane was used as a separator, a short circuit occurred in 250 cycles.

Regarding the ion conductive membranes of the above Examples and Comparative Examples, the air permeability value T (s), the puncture strength F (N), the density ρ (g / cm ³ ), the average film thickness L (μm), and the above formula (1). The X value represented by) and the measurement result are shown in Table 1. In Table 1, ◯ indicates that a life of 300 cycles or more was observed, and × indicates that the positive and negative electrodes were short-circuited in less than 300 cycles.

From the results of the examples, the following was found.
The ion conductive film having an X value of 200 or more represented by the above formula (1) can be suitably used, for example, as a separator, an electrolyte, a protective agent for electrodes, etc. of a storage battery composed of a zinc negative electrode. It was demonstrated that the storage battery can have a long life.
In the above embodiment, as the ionic conductive film, a microporous film in which four sheets are laminated is used, or a specific fluorine atom-containing polymer, a conjugated diene polymer, or a (meth) acrylic polymer is used. An ionic conductive membrane obtained by kneading with a specific layered double hydroxide is used, but the ionic conductive membrane of the present invention has an X value of 200 represented by the above formula (1). As described above, when used as a separator, an electrolyte, a protective agent for electrodes, etc., the above-mentioned ionic conduction performance and performance of suppressing the growth of dendrite can be exhibited.

In Example 1, as compared with Comparative Example 2, four microporous membranes were used in layers instead of using only one. By forming the microporous membrane in a laminated structure in this way, the positions of the through holes are displaced for each layer, and the air permeability value and the puncture strength are increased. As a result, the X value becomes 200 or more, the effect of the present invention of preventing a short circuit between the electrodes due to the growth of dendrites can be exhibited, and the battery life is extended.

In Example 2, the average film thickness of the ionic conductive film was changed from 50 μm to 100 μm as compared with Comparative Example 3, and by increasing the average film thickness in this way, the performance changed in total, resulting in a result. The X value is 200 or more, the effect of the present invention of preventing short circuits between electrodes due to the growth of dendrites can be exhibited, and the life of the battery is extended.
In Example 3, the kneading time at 30 ° C. was set to 3 to 5 minutes and the average film thickness was set to 100 μm to 300 μm as compared with Example 2. By lengthening the kneading time in this way, the kneading time was set to 3 to 5 minutes. The fibrosis of PTFE is promoted, the resulting ionic conductive film becomes denser, and the air permeability value and puncture strength increase. Coupled with the increase in the average film thickness, the X value becomes larger, the effect of the present invention of preventing short circuits between electrodes due to the growth of dendrites becomes more remarkable, and the battery life is extended.

In Example 4, the kneading temperature was set to 30 ° C. to 50 ° C. as compared with Example 3, and by raising the kneading temperature in this way, the fibrosis of PTFE was promoted and the obtained ion conduction was obtained. The sex membrane becomes denser, and the air permeability value and puncture strength increase. As a result, the X value becomes larger, the effect of the present invention of preventing short circuits between electrodes due to the growth of dendrites becomes more remarkable, and the battery life is extended.

In Example 5, the kneading time at 50 ° C. was set to 5 to 10 minutes as compared with Example 4, and by lengthening the kneading time in this way, the fibrosis of PTFE was promoted and obtained. The ion-conducting membrane to be formed becomes denser, and the air permeability value and the puncture strength become larger. As a result, the X value becomes larger, the effect of the present invention of preventing short circuits between electrodes due to the growth of dendrites becomes more remarkable, and the battery life is extended.

In Example 6, as compared with Example 5, an ionic conductive film having an average film thickness of 100 μm was prepared by rolling after kneading, and by performing the rolling step in this way, the fiberization of PTFE was achieved. It is promoted and the obtained ionic conductive film becomes denser, and the air permeability value and the puncture strength become larger. As a result, a large X value is achieved with a thin average film thickness, and the battery life is extended.

In Example 7, a styrene-butadiene copolymer is mainly used as the polymer in the ionic conductive membrane, and PTFE and carboxymethyl cellulose are mainly used. Example 10 is the same as that of Example 7 except that an acrylonitrile-butadiene copolymer is used instead of the styrene-butadiene copolymer as the polymer in the ionic conductive membrane. By using the conjugated diene polymer in this way, an ionic conductive film that does not allow gas to pass through is formed, and the air permeability value becomes very large. As a result, a large X value is achieved and the battery life is extended. Further, Example 11 is the same as that of Example 7 except that the compounding ratio is changed in the preparation of the ion conductive film, but when the X value is 200 or more, the battery life is extended.

In Example 8, a (meth) acrylic polymer prepared by using a polyfunctional monomer is used as the polymer in the ionic conductive membrane, and carboxymethyl cellulose is used as the other polymer. In Example 9, as the polymer in the ionic conductive membrane, a (meth) acrylic type prepared by using only a monofunctional monomer instead of the (meth) acrylic type polymer prepared by using a polyfunctional monomer. This is the same as in Example 8 except that the polymer is used. By using the (meth) acrylic polymer in this way, an ionic conductive film that does not allow gas to pass through is formed, and the air permeability value becomes very large. As a result, a large X value is achieved and the battery life is extended. Further, in Example 12, carboxymethyl cellulose was not used as another polymer in the preparation of the ionic conductive membrane, and Example 8 was carried out except that the blending ratio was changed and the treatment method of the kneaded product was changed. However, when the X value is 200 or more, the life of the battery is extended.

As described above, in all the examples in which the X value is 200 or more, the life of 300 cycles or more is observed, and in all the comparative examples in which the X value is less than 200, the life is positive in less than 300 cycles (250 cycles or less). The negative electrode was short-circuited. If a life of 300 cycles or more can be achieved as in the embodiment, for example, it can be used for a long period of time without replacing the battery (for example, it can be charged once a day and used for about 1 year) as an industrial product. It will be significantly better.

Therefore, from the results of the above-mentioned examples, it can be said that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in the present specification, and advantageous actions and effects can be exhibited.

Claims (5)

The following formula (1):

(In the formula, T represents the air permeability value (s). F represents the puncture strength (N). Ρ represents the density (g / cm ³ ). L represents the average film thickness (μm). The X value represented by) is 200 or more, and
It contains a polymer and a compound containing at least one element selected from Groups 1 to 17 of the Periodic Table.
The compound is an ionic conductive film , which is at least one compound selected from the group consisting of oxides, hydroxides, layered double hydroxides, phosphoric acid compounds, and sulfuric acid compounds. .. The polymer is characterized by containing at least one polymer selected from the group consisting of a halogen atom-containing polymer, a rubber-like polymer having an unsaturated carbon bond in the main chain, and a (meth) acrylic polymer. The ion conductive film according to claim 1 . The ion conductive membrane according to claim 1 or 2 , which has a structure in which a plurality of layers are laminated. A battery component comprising the ion conductive film according to any one of claims 1 to 3 . A battery characterized by being configured by using the battery component according to claim 4 .