JP6718258B2 - Anion conducting membrane - Google Patents

Description

The present invention relates to anion conducting membranes. More specifically, the present invention relates to an anion conductive membrane that can be suitably used as a separator for batteries and the like.

In recent years, the importance of batteries is rapidly increasing in many industries, from small portable devices to large-scale applications such as automobiles. A new battery system that has an advantage mainly in terms of its capacity, energy density and secondary battery conversion. Has been variously developed and improved. For example, a zinc negative electrode using a zinc species as a negative electrode active material has been studied for a long time with the spread of batteries, and in particular, an air/zinc primary battery, a manganese/zinc primary battery, and a silver/zinc primary battery have been put into practical use. Widely used in the world.
However, when zinc is used for the negative electrode of the storage battery, there is a problem that the positive electrode and the negative electrode are short-circuited by the dendrite formed on the surface of the negative electrode during charging, and the battery cannot be charged or discharged.

Many technical developments have been made to solve such problems. For example, a positive electrode, a negative electrode containing at least one of zinc and a zinc compound as a negative electrode active material, and an ion-exchange formed on the negative electrode or the negative electrode active material. At least one selected from the group consisting of the negative electrode, the coating, and the electrolyte, which has a coating containing a resin and an electrolyte containing an alkaline aqueous solution as an electrolytic solution, is more noble than the standard electrode potential of zinc and contains zinc. Disclosed is an alkaline secondary battery containing at least one selected from the group consisting of a metal having a melting point lower than the melting point, an oxide containing the metal, a salt containing the metal, and an ion containing the metal. (For example, refer to Patent Document 1). And, a zinc negative electrode active material for a zinc-alkali secondary battery coated with a hydroxide that does not exhibit substantial solubility in an alkaline aqueous solution and does not accompany an oxidation/reduction reaction in the potential range of the charge/discharge reaction of the battery is disclosed. (For example, refer to Patent Document 2). Further, a technique is disclosed in which a separator is formed by an anion conductive material containing a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table to suppress dendrites. (For example, refer to Patent Documents 3 to 5).
A technique of using a material similar to the anion conductive material as a negative electrode mixture of a lithium ion secondary battery is disclosed (for example, see Patent Document 6).

JP, 2013-54877, A JP-A-5-144431 International Publication No. 2014/119665 JP, 2005-15229, A JP, 2005-95286, A JP, 2013-134896, A

As described above, various methods have been developed for suppressing the short circuit between the positive electrode and the negative electrode and prolonging the life of the battery in a battery using a zinc species or the like that generates dendrite as an active material. There is a need for longer life, and further development of materials that can extend the life of batteries is required.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a material that can further extend the service life of a battery that uses a zinc species or the like that generates dendrite as an active material.

The present inventor has variously studied materials that can further extend the life of a battery using a zinc species or the like that generates dendrites as an active material, and an anion conductive membrane containing a binder polymer and a layered double hydroxide. We focused on using. In such an anion conductive membrane, the layered double hydroxide portion selectively permeates hydroxide ions, and the binder polymer suppresses the growth of dendrites. Further, the present inventor has formed an anion conductive membrane containing a binder polymer and a layered double hydroxide, and further containing an anionic surfactant component. The present inventor has used this anion conductive film as a battery separator because it has excellent electrochemical properties (sufficient electronic insulating property and ionic conductivity) as a separator, but is superior in mechanical strength. In this case, since it is possible to more sufficiently prevent a short circuit between the positive electrode and the negative electrode due to the growth of dendrites, it was found that the battery can have a long life, and it was conceived that the above problems can be successfully solved. The present invention has been reached. It is considered that such an anion conductive membrane having excellent mechanical strength is suitable also from the viewpoint of production (rolling into a roll, incorporation into a battery or the like).

That is, the present invention is an anion conductive membrane containing a binder polymer, a layered double hydroxide, and an anionic surfactant component.
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.

<Anion conductive membrane>
The anion-conductive membrane of the present invention contains a binder polymer, a layered double hydroxide, and an anionic surfactant component. The reason why the anion-conductive membrane of the present invention has excellent mechanical strength is considered as follows. In a material for forming an anion conductive film (hereinafter, such a material before film formation is also referred to as an anion conductive film forming material), layered double hydroxides having low dispersibility in a binder polymer are aggregated. doing. It is considered that when the layered double hydroxides agglomerate with each other, voids due to the agglomeration are formed, so that the film strength decreases. This problem itself has been newly discovered by the present inventor. Here, when an anionic surfactant component is added to the anion-conductive film-forming material, the anionic surfactant component is easily adsorbed on the surface of the layered double hydroxide, and the primary double layered hydroxide is Electrostatic repulsion between the particles makes the layered double hydroxide finer and suppresses its aggregation.
Hereinafter, each component will be described.

(Anionic surfactant component)
The anionic surfactant component is a component that has a hydrophilic group and a hydrophobic group and can function as a surfactant regardless of the purpose of use, and the hydrophilic group is an anionic group. Means all of. That is, the anionic surfactant component may also have other functions. Examples of the purpose of use include the purpose of use as a dispersant, a wet penetrant, and the like.

Examples of the hydrophilic group of the anionic surfactant component include a carboxylic acid (salt) group, a carboxylic acid ester group, a sulfonic acid (salt) group, a sulfonic acid ester group, and a phosphoric acid (salt) group. Among them, the anionic surfactant component preferably has at least one functional group selected from the group consisting of a sulfonic acid (salt) group, a sulfonic acid ester group, and a phosphoric acid (salt) group. Examples of the atom or atomic group forming a salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as calcium and magnesium; trivalent metal atoms such as aluminum. Ammonium and the like can be mentioned.

Examples of the hydrophobic group of the anionic surfactant component include an alkyl group, an aryl group, a polyoxyalkylene group, an alkenyl group, and a group in which two or more kinds of these groups are bonded.
The number of carbon atoms in the hydrophobic group is, for example, preferably 3 or more, more preferably 6 or more, and further preferably 12 or more. Further, the carbon number is preferably 30 or less, and more preferably 24 or less.

Examples of the anionic surfactant include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; sodium dodecyl benzene sulfonate and dodecyl dodecyl. Alkyl aryl sulfonate salts such as ammonium benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl phenyl ether sulfate ester salts; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulphate salts; polyoxyethylene alkyl aryl sulphate salts; dialkyl Sulfosuccinate; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate ester salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphonate salt, Sulfuric acid ester having an allyl group such as sulfonate salt of allyloxymethylalkyloxypolyoxyethylene or a salt thereof; sulfuric acid ester salt of allyloxymethylalkoxyethyl polyoxyethylene; arylsulfonic acid-formalin condensate and the like. One kind or two or more kinds can be used.

As the anionic surfactant, it is also possible to use a reactive surfactant which reacts with a monomer component used as a raw material of the binder polymer to form a part of the binder polymer. That is, the anionic surfactant component may be an ordinary surfactant (a compound different from the binder polymer) or a constituent unit that constitutes a part of the binder polymer. It is preferable that it is a compound other than.

Among them, the anionic surfactant is preferably an alkylaryl sulfonate salt, more preferably dodecylbenzene sulfonate, and even more preferably sodium dodecylbenzene sulfonate.

The content of the anionic surfactant component in 100% by mass of the anion conductive membrane of the present invention is preferably 0.01% by mass or more from the viewpoint of further improving the effect of the present invention, It is more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more. Further, the content is such that the viscosity of the kneaded material at the time of kneading the anion-conductive film-forming material is sufficient and the components contained in the anion-conductive film-forming material are in a more uniform state, and battery characteristics. From the viewpoint of further improving the above, the content is preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less.

In the present specification, the content of the anionic surfactant component is the total amount of the anionic surfactant (a compound different from the binder polymer) and the constituent units derived from the compound in the binder polymer. Is. In other words, the content of the component is the total amount of all the anionic surfactants used in obtaining the anion conductive membrane of the present invention. The timing of the addition of the anionic surfactant component contained in the anion-conductive membrane of the present invention is not particularly limited, and for example, a trace amount as an emulsifying agent for emulsion polymerization is added to an aqueous dispersion of a binder polymer which is a commercially available product. Although it may be contained, it may be further added to the water dispersion, and by further adding the content of the component within the above preferable range, The effect of the present invention becomes more excellent.

(Binder polymer)
The binder polymer may be any one capable of thickening the anion-conductive film-forming material and binding the components in the material, for example, an aliphatic hydrocarbon group-containing polymer such as polyethylene, polystyrene. An aromatic group-containing polymer such as alkylene glycol; an ether group-containing polymer such as alkylene glycol; a hydroxyl group-containing polymer such as polyvinyl alcohol; an amide group-containing polymer such as polyacrylamide; an imide group-containing polymer such as polymaleimide; a (meth)acrylic polymer; Halogen atom-containing polymers such as polyvinylidene fluoride and polytetrafluoroethylene; ammonium salt-containing polymers; phosphonium salt-containing polymers; ion-exchange polymers; natural rubber; conjugated diene-based polymers; hydroxyalkyl celluloses (eg hydroxyethyl cellulose), etc. Examples of the saccharide include amino group-containing polymers such as polyethyleneimine, and one of these may be used, or two or more thereof may be used. When these polymers have a functional group, it may have it in the main chain and/or side chain, and may be present as a binding site with the crosslinking agent. Further, the binder polymer may be crosslinked with an organic crosslinking agent compound.

The binder polymer preferably has a weight average molecular weight of 10,000 or more and 6.5 million or less. The weight average molecular weight is more preferably 20,000 or more. The weight average molecular weight can be measured as a polystyrene-converted weight average molecular weight by gel permeation chromatography (GPC) under the following conditions.
Equipment: Tosoh Corporation HCL-8220GPC
Column: TSKgel Super AWM-H
Eluent (LiBr.H ₂ O, NMP containing phosphoric acid): 0.01 mol/L

The glass transition temperature (Tg) of the binder polymer is preferably −40° C. or higher and 50° C. or lower. This is because when the Tg of the binder polymer is less than -40°C, the mechanical strength of the anion-conductive membrane is insufficient and the dendrite suppressing effect may be reduced. If the Tg exceeds 50° C., the anion-conductive membrane becomes too hard and brittle, and the anion-conductive membrane may be cracked during the formation of the battery, which may reduce the life performance of the battery. .. In the anion-conductive film of the present invention, in order to suppress the formation of voids due to the aggregation of the layered double hydroxide, the components contained in the anion-conductive film-forming material are sufficiently kneaded. It is preferable that the aggregation of the layered double hydroxide is suppressed and the components other than the layered double hydroxide and the layered double hydroxide are brought into a uniform state. When the Tg of the binder polymer is −40° C. or higher and 50° C. or lower, the kneaded product at the time of kneading with the layered double hydroxide has more appropriate fluidity and crushes the aggregates of the layered double hydroxide. Alternatively, the components contained in the anion conductive film forming material can be made more uniform. The Tg of the binder polymer is more preferably −15° C. or higher and 30° C. or lower, and even more preferably −10° C. or higher and 20° C. or lower.
As for the Tg of the binder polymer, a polymer film was formed by applying the polymer to a glass plate and drying at 120° C. for 1 hour, and the obtained polymer film was analyzed by a differential scanning calorimeter (device name: thermal analysis device DSC3100S, BRVKER).

Above all, the binder polymer is preferably a conjugated diene polymer and/or a (meth)acrylic polymer.
The anion conductive membrane of the present invention containing a conjugated diene-based polymer and/or a (meth)acrylic polymer suppresses the permeation of metal ions such as zincate ions and allows the hydroxide ions to pass therethrough. Since it is a membrane having selective permeability and having few voids, the battery can have a longer life by using this membrane as a separator. Since the anion conductive film formed by using the conjugated diene polymer has alkali resistance, it can be suitably used as a material for a battery separator that comes into contact with an alkaline electrolyte. Further, since the conjugated diene polymer is relatively hydrophobic and easily aggregates, in the anion conductive membrane of the present invention, this aggregation can be sufficiently disintegrated by the action of the anionic surfactant.

<Conjugated diene polymer>
The conjugated diene-based polymer is not particularly limited as long as it has a monomer unit derived from a conjugated diene monomer, but it is preferably one having a monomer unit derived from an aromatic vinyl monomer. Thereby, the effect of the present invention becomes more remarkable.

The conjugated diene-based monomer is preferably an aliphatic conjugated diene-based monomer. Examples of the aliphatic conjugated diene-based monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene and the like, among which 1,3-butadiene is preferable. The conjugated diene-based monomer may be used alone or in combination of two or more kinds.

The conjugated diene-based polymer may be a homopolymer such as polybutadiene or polyisoprene, or may be a copolymer, for example, a copolymer is preferable, and among them, an aromatic vinyl monomer. It is more preferable that the copolymer further has a monomer unit derived from it.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-methoxy. Styrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chloro. Styrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene, m-tert-butoxystyrene. , P-tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, vinyltoluene and the like. Among these, styrene and α-methylstyrene are preferable because they can increase the heat resistance and mechanical strength of the anion conductive membrane. These aromatic vinyl monomers may be used alone or in combination of two or more kinds.

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

From the viewpoint of making the effect of the present invention more remarkable, the conjugated diene-based polymer is preferably a styrene-butadiene-based copolymer or an acrylonitrile-butadiene-based copolymer, more preferably a styrene-butadiene-based copolymer. ..

The conjugated diene-based polymer may have a monomer unit derived from another unsaturated monomer other than the monomer unit derived from the aliphatic conjugated diene monomer and the monomer unit derived from the aromatic vinyl monomer.

Examples of the other unsaturated monomer include acid group-containing vinyl monomers such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamidomethylpropanesulfonic acid, and styrenesulfonate; methyl (meth)acrylate; Ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylic (Meth)acrylic acid ester monomers such as hexyl acid salt, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate; Hydroxy group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, nitrile group-containing vinyl monomers such as (meth)acrylonitrile, (meth)acrylamide, N-methylol (meth)acrylamide, N-ethylol (meth)acrylamide, dimethyl (meth)acrylamide, diethyl (meth)acrylamide and other (meth)acrylamide monomers, divinylbenzene, ethylene glycol dimethacrylate, isopropylene glycol diacrylate, tetramethylene glycol dimethacrylate, etc. Functional vinyl monomers; vinyl monomers containing an alkoxysilane group such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane can be mentioned, and one or two of these can be mentioned. The above can be used.

In 100% by mass of the conjugated diene-based polymer, the mass ratio of the monomer unit derived from other unsaturated monomer is preferably 40% by mass or less, more preferably 20% by mass or less, and 10% by mass or less. It is more preferable that the amount is 5% by mass or less.

<(Meth)acrylic polymer>
In the present specification, the above-mentioned (meth)acrylic polymer means a polymer that does not have a monomer unit derived from a conjugated diene monomer, but has a structural unit derived from a (meth)acrylic monomer. The (meth)acrylic monomer means a monomer having an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or an atomic group, or a derivative of such a monomer.

The (meth)acrylic polymer is preferably a (meth)acrylic acid polymer. The (meth)acrylic acid-based polymer refers to a polymer having a structural unit derived from a (meth)acrylic acid-based monomer, and the (meth)acrylic acid-based monomer is an acryloyl group or a methacryloyl group, or hydrogen in these groups. It has a group in which an atom is replaced with another atom or atomic group, and has a carboxylic acid group (-COOH group), a carboxylic acid group (-COOM group), or an acid anhydride group thereof (-C(=O)). It is a monomer having a —O—C(═O)— group. The above M represents a metal salt, an ammonium salt, or an organic amine salt. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as calcium and magnesium; trivalent metals such as aluminum and iron. Atoms are preferred. As the organic amine forming the organic amine salt, alkanolamines such as ethanolamine, diethanolamine and triethanolamine, and triethylamine are preferable. The (meth)acrylic acid-based monomer is preferably (meth)acrylic acid (salt). (Meth)acrylic acid (salt) is a monomer having an acryloyl group or a methacryloyl group and a carboxylic acid group (—COOH group) or a carboxylic acid group (—COOM group).

For example, it is preferable that the monomer component for obtaining the (meth)acrylic acid-based polymer contains a (meth)acrylic acid-based monomer and another copolymerizable unsaturated monomer.

In 100% by mass of the (meth)acrylic acid-based polymer, the content of the monomer unit derived from the (meth)acrylic acid-based monomer is 0.1 to 5% by mass, and the content of the monomer unit derived from the other copolymerizable unsaturated monomer is The content is preferably 95 to 99.9% by mass. The content of the monomer unit derived from the (meth)acrylic acid-based monomer is 0.3% by mass or more, and the content of the monomer unit derived from another copolymerizable unsaturated monomer is 99.7% by mass or less. More preferably, the content of the monomer unit derived from the (meth)acrylic acid-based monomer is 0.5% by mass or more, and the content of the monomer unit derived from another copolymerizable unsaturated monomer is 99.5% by mass or less. More preferably. Within such a range, the monomer components are stably copolymerized.

Examples of other copolymerizable unsaturated monomers include (meth)acrylic monomers other than (meth)acrylic acid-based monomers, unsaturated monomers having an aromatic ring, and other copolymerizable unsaturated monomers.
Examples of the (meth)acrylic monomer other than the (meth)acrylic acid-based monomer include, for example, an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or an atomic group. And a monomer having a carboxylic acid ester group or a derivative of such a monomer.

Examples of the (meth)acrylic monomer having a carboxylic acid ester group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate. , Isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl Methacrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diallyl phthalate, triallyl cyanurate, ethylene glycol diacrylate, ethylene glycol di Methacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, allyl acrylate, allyl Methacrylate and the like; esterified products of (meth)acrylic acid-based monomers other than these, and the like, and it is preferable to use one or more of these.

In 100% by mass of the (meth)acrylic acid-based polymer, the content of monomer units derived from a (meth)acrylic-based monomer other than the (meth)acrylic acid-based monomer is preferably 20% by mass or more, and 40% by mass. % Or more, and more preferably 60% by mass or more. The content of monomer units derived from a (meth)acrylic monomer other than the (meth)acrylic acid-based monomer is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less. preferable.

Examples of the unsaturated monomer having an aromatic ring include divinylbenzene, styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene and the like, and preferably styrene.
That is, it is also one of preferred embodiments of the present invention that the (meth)acrylic acid-based polymer is a styrene (meth)acrylic acid-based polymer obtained from a monomer component containing styrene. With such a form, the effects of the present invention can be sufficiently exhibited while reducing the cost.

The content of the monomer unit derived from the unsaturated monomer having an aromatic ring in 100% by mass of the (meth)acrylic acid-based polymer is preferably 1% by mass or more, and more preferably 5% by mass or more. It is more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 40% by mass or more. Further, the content of the monomer unit is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less. An unsaturated monomer having an aromatic ring may not be used as a monomer component that is a raw material of the (meth)acrylic acid-based polymer.

Examples of the other copolymerizable unsaturated monomer include acrylonitrile and polyfunctional unsaturated monomers such as trimethylolpropane diallyl ether.

The binder polymer can be produced, for example, by polymerizing a monomer component forming a constituent unit contained in the above-mentioned polymer.
The method for polymerizing the monomer component is not particularly limited, and examples thereof include an aqueous solution polymerization method, an emulsion polymerization method, a reverse phase suspension polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. Among these methods, the emulsion polymerization method is preferably used from the viewpoint of easy production. When an emulsion polymerization method is used as a method for polymerizing the above-mentioned monomer component, the emulsion polymerization is performed after mixing the monomer component, the surfactant, and a dispersion medium containing water as the main component (hereinafter, also referred to as an aqueous dispersion medium). May be carried out, by emulsification by stirring the monomer component, the surfactant, and the aqueous dispersion medium, emulsion polymerization may be carried out after preparing a pre-emulsion, the monomer component, the surfactant, and the aqueous dispersion. Emulsion polymerization may be carried out by mixing at least one type (a part of) of the medium with the remaining pre-emulsion. As the surfactant, the anionic surfactant according to the present invention can be used, and also a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. The monomer component, the surfactant, and the aqueous dispersion medium may be added all at once, may be added in portions, or may be continuously added dropwise.

A polymerization initiator can be used for the polymerization of each of the above monomer components. As the polymerization initiator, those which are usually used can be used and are not particularly limited as long as they generate a radical molecule 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-methylpropionamidine], 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-butyl hydroperoxide and rongalite, potassium persulfate and metal salts, redox initiators such as ammonium persulfate and sodium bisulfite, and the like, 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 more preferably 0.05% by mass or more, based on 100% by mass of all the monomer components used as the raw material of the binder polymer. More preferable. The amount used is preferably 2% by mass or less, and more preferably 1% by mass or less.

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

The content of the binder polymer is preferably 10% by mass or more and more preferably 15% by mass or more in 100% by mass of the anion conductive film from the viewpoint of mechanical strength and ion conductivity of the anion conductive film. Is more preferable, 20% by mass or more is further preferable, and 25% by mass or more is particularly preferable. Further, the content is preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

(Layered double hydroxide)
The layered double hydroxide is represented by the following general 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. A ^n- represents an anion having a valence of 1 or more and a valence of 3 or less, such as OH ⁻ , Cl ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , and COO ⁻ . Is a number of 0 or more, n is a number of 1 or more and 3 or less, and x is a number of 0.20 or more and 0.40 or less). It is preferable that A ⁿ⁻ represents a divalent or less anion.
Such layered double hydroxides are naturally-occurring ones (for example, hydrotalcite, Manasseite, Motucoreite, Stichtite, Sjogrenite, Barbartite Bartbert). , Pyroaurite, Iomaite, Chlormagaluminite, Hydrocalmite, Green Rust 1, Greenberry 1, Berthierine, Tacobite, Tacobite, Tacobite Reevesite), honesite (Honessite), eardlite (Eardlyite), Meixnerite (Meixnerite), etc.), as well as artificially synthesized ones. It may be a dehydrated compound, a compound obtained by decomposing an anion in the interlayer, or a compound obtained by exchanging an anion in the interlayer with a hydroxide ion.
The layered double hydroxide is preferably a Mg-Al-based layered double hydroxide, and more preferably hydrotalcite.

The layered double hydroxide is preferably in the form of particles, and examples of the shape thereof include fine powder, powder, granules, scales, polyhedra, rods, and curved surface-containing shapes. Incidentally, the particles having an average particle diameter in the range as described below are, for example, a method of pulverizing the particles by a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle diameter, and then drying. In addition to a method of selecting the particle size by sieving the coarse particles, a method of obtaining particles having a desired particle size by optimizing preparation conditions in the step of manufacturing particles can be used.

The layered double hydroxide preferably has an average particle size of 5 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. On the other hand, the average particle diameter is preferably 0.001 μm or more, more preferably 0.01 μm or more.
The average particle diameter can be measured by a laser diffraction method.

The content of the layered double hydroxide is not particularly limited as long as it is an amount capable of expressing anion conductivity in the anion conductive membrane of the present invention, but is 30 mass% in 100 mass% of the anion conductive membrane. The above is preferable. Thereby, the mechanical strength and ionic conductivity of the anion-conductive membrane can be improved. The mass ratio is more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. The mass ratio is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.

The anion-conductive film of the present invention may contain an acid group-containing polymer described below and other components as long as they contain a binder polymer, a layered double hydroxide and an anionic surfactant.

(Polymer containing acid group)
The anion conductive membrane of the present invention preferably further contains an acid group-containing polymer. Due to the steric hindrance of the acid group-containing polymer, the re-aggregation of the layered double hydroxide in the anion-conductive film-forming material can be prevented, the dispersion stability can be further improved, and the mechanical strength of the obtained film is better. Will be things.
The acid group-containing polymer is a polymer having an acid group such as a carboxylic acid (salt) group or a sulfonic acid (salt) group, and is different from the binder polymer contained in the anion conductive membrane of the present invention. However, from the viewpoint of further improving the dispersion stability of the layered double hydroxide, those mainly composed of a monomer unit derived from an acid group-containing monomer are preferable. The term “mainly constituted” means that the monomer unit derived from the acid group-containing monomer is 50 mol% or more in 100 mol% of all the monomer units. The monomer unit derived from the acid group-containing monomer in 100 mol% of all monomer units is more preferably 60 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, and 90 mol% or more. Is particularly preferable. Examples of the acid group-containing polymer include carboxyl group-containing polymers such as poly(meth)acrylic acid, polymaleic acid, polyitaconic acid, polymethylene glutaric acid, and carboxymethyl cellulose; poly(meth)acrylic acid salts, polymaleic acid salts, polyitacones. Suitable examples include carboxylic acid salt-containing polymers such as acid salts and polymethylene glutaric acid salts; sulfonate moiety-containing polymers and the like, and one or more of these can be used.
Among them, the acid group-containing polymer is more preferably a carboxyl group-containing polymer or a carboxylate-containing polymer. Among them, poly(meth)acrylic acid, poly(meth)acrylic acid salt, polymaleic acid, polymalein Acid salts, polyitaconic acid, and polyitaconate salts are more preferable, and from the viewpoint of broadening the molecular chain of the acid-containing group polymer and making the components contained in the anion-conductive film-forming material more uniform, polyacryl Acid salts, polymaleic acid salts and polyitaconic acid salts are particularly suitable. Examples of the atom or atomic group forming the salt include sodium, potassium, ammonium and the like.

The acid group-containing polymer preferably has a weight average molecular weight of 1,000 or more and 6.5 million or less. The weight average molecular weight is more preferably 2000 or more. Further, the weight average molecular weight is more preferably 2,000,000 or less. The weight average molecular weight can be measured by the same method as the method for measuring the weight average molecular weight of the binder polymer.

The content of the acid group-containing polymer in 100% by mass of the anion-conductive membrane of the present invention is preferably 0.01% by mass or more, and more preferably from the viewpoint of making the effect of the present invention more remarkable. Is 0.02% by mass or more, and more preferably 0.05% by mass or more. Further, the content makes the anionic conductive film a desirable electrochemical characteristic as a separator, and also makes the viscosity of the kneaded material at the time of kneading the anionic conductive film forming material sufficient to obtain the anionic conductive film forming material. From the viewpoint of making the components contained in (1) more uniform, the content is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.

The acid group-containing polymer contained in the anion-conductive membrane of the present invention is not particularly limited in the timing of its addition, and for example, it is contained in a trace amount in a commercially available binder polymer aqueous dispersion. However, it may be further added to the water dispersion, and by controlling the content within the above preferable range, the effect of the present invention becomes more remarkable.

(Other ingredients)
The above-mentioned other components refer to solid contents other than the above-mentioned binder polymer, layered double hydroxide, anionic surfactant, and acid group-containing polymer. Examples of the other components include polymers other than the binder polymer and the acid group-containing polymer, inorganic compounds other than layered double hydroxide, carbon, ceramics, cationic surfactants, nonionic surfactants, amphoteric surfactants. And the like, and one or more of these can be used.

The content of the other components is preferably 20% by mass or less, and more preferably 10% by mass or less, with respect to 100% by mass of the anion-conductive film, from the viewpoint of material uniformity and film formability. is there.
When two or more kinds of the other components are included, the content is the total amount of the other components.

The average film thickness of the anion conductive film of the present invention is preferably 10 μm or more and 1000 μm or less. If the thickness is less than 10 μm, many damages may occur during film formation. Further, if it is thicker than 1000 μm, it is disadvantageous from the viewpoint of cost, and there is a possibility that the ability of permeating hydroxide ions may be lowered. The average film thickness is more preferably 20 μm or more. Further, the average film thickness is more preferably 500 μm or less.
The average film thickness is calculated by measuring an arbitrary 10 points of the film using a Digimatic micrometer (manufactured by Mitutoyo Co., Ltd.) and calculating the average value.

The anion-conductive film of the present invention can be obtained by preparing an anion-conductive film forming material and molding the obtained anion-conductive film forming material into a film.
Examples of the method for preparing the anion-conductive film-forming material in the present invention include the following methods.
If necessary, an acid group-containing polymer and other components are mixed with the binder polymer, layered double hydroxide, and anionic surfactant component. A mixer, a blender, a kneader, a bead mill, a ready mill, a roll mill, a ball mill, or the like can be used for mixing. Upon mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran, N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be used as a medium.
When the binder polymer forms emulsion particles, at least a part of the anionic surfactant component may form emulsion particles as an emulsifier.

The content ratio of the medium such as the aqueous dispersion medium in the anion-conductive film-forming material of the present invention is 20% by mass or more and 60% by mass in 100% by mass of the anion-conductive film-forming material from the viewpoint of suppressing film shrinkage during molding. The following is preferable. The content ratio is more preferably 25% by mass or more and 50% by mass or less.
When the binder polymer, the acid group-containing polymer, the anionic surfactant and the like contained in the anion conductive film forming material are in the form of a dispersion medium or a solution, the dispersion medium and solvent used are also included in the medium.

The method for producing an anion conductive film from the anion conductive film forming material is not particularly limited, a method of rolling the anion conductive film forming material with a roll to form a film, a film rolled with a flat plate press or the like. It is possible to use a method of forming into a film shape, a method of forming into a film shape such as an injection molding method, an extrusion molding method, a cast method or the like. These molding methods may be used alone or in combination of two or more.
A method for producing an anion-conductive membrane in this manner, that is, an anion-conducting membrane-forming step of forming an anion-conductive film-forming material containing a binder polymer, a layered double hydroxide and an anionic surfactant component into a film-like shape The method for producing a flexible film is also one aspect of the present invention. As the anion conductive film forming material used in this manufacturing method, the above-mentioned materials are preferable, and the anion conductive film to be manufactured is also preferably the above-described anion conductive film of the present invention.

The above-mentioned manufacturing method preferably includes a step of heating the membrane after the step of molding the anion-conductive membrane forming material into a membrane shape. Thereby, the anion conductive film can be efficiently formed.
In the heat treatment after film formation, the heating temperature may be set appropriately, but may be, for example, 60° C. or higher and 180° C. or lower. The heating temperature is preferably 160° C. or lower, and more preferably 150° C. or lower. Further, the heating temperature may be changed stepwise. By setting such a temperature range, it is possible to prolong the service life of the battery configured by using the anion conductive membrane as the separator.
The heating time within the above temperature range can be, for example, 10 minutes or more and 12 hours or less.
The heating temperature is preferably 1 hour or more. The heating time is preferably 6 hours or less.

<Separator>
The anion-conductive membrane of the present invention can be suitably used as a battery separator, and by using such a separator, the battery life can be extended.
Such a separator including the anion conductive membrane of the present invention is also one aspect of the present invention.

<Battery>
A battery constructed using the separator of the present invention is also one aspect of the present invention.
In the battery of the present invention, the anion-conductive membrane functions as a separator, but another separator may be laminated on the anion-conductive membrane of the present invention and used.
Examples of such another separator include nonwoven fabric, filter paper, polyolefin resin such as polyethylene and polypropylene, fluorine atom-containing resin such as polytetrafluoroethylene and polyvinylidene fluoride, cellulose, fibrillated cellulose, viscose rayon, cellulose acetate, hydroxy. Aryl group-containing resins such as alkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polystyrene, polyacrylonitrile resin, polyacrylamide resin, polyamide resin, polyimide resin, (meth)acrylic resin, polyisoprenol and poly(meth)allyl alcohol Containing resin, polycarbonate resin, polyester resin, polyurethane resin, agar, organic-inorganic composite resin, ion exchange resin, sulfonate containing resin, quaternary ammonium salt containing resin, quaternary phosphonium salt containing resin, cycloolefin polymer, ceramics, etc. A film made of an inorganic material or the like can be used. These separators may be used alone or in combination of two or more.

As the positive electrode active material constituting the battery of the present invention, those usually used as the positive electrode active material of the primary battery or the secondary battery can be used, and are not particularly limited, but, for example, oxygen (oxygen is the positive electrode active material In that case, the positive electrode contains a perovskite compound capable of reducing oxygen or oxidizing water, a cobalt-containing compound, an iron-containing compound, a copper-containing compound, a manganese-containing compound, a vanadium-containing compound, a nickel-containing compound, an iridium-containing compound, a platinum-containing compound. Compounds; palladium-containing compounds; gold-containing compounds; silver-containing compounds; air electrodes composed of carbon-containing compounds, etc.); nickel-containing compounds such as nickel oxyhydroxide, nickel hydroxide, cobalt-containing nickel hydroxide; manganese dioxide Manganese-containing compounds such as; silver oxide; lithium-containing compounds such as lithium cobalt oxide; iron-containing compounds; zinc species such as metallic zinc and zinc oxide.
Among these, it is one of the suitable embodiments of the present invention that the positive electrode active material is a nickel-containing compound or a zinc species.
A battery in which the positive electrode active material is oxygen, such as an air battery or a fuel cell, is also one of the preferred embodiments of the present invention.

As the negative electrode active material constituting the battery of the present invention, carbon, lithium, sodium, magnesium, zinc, nickel, tin, cadmium, hydrogen storage alloy, silicon-containing materials, etc., which are usually used as the negative electrode active material of the battery are used. Can be used. Among these, from the viewpoint of sufficiently exhibiting the characteristics of the anion-conductive membrane of the present invention, active materials that easily generate dendrites, such as lithium species, magnesium species, zinc species, nickel species, and cadmium species, are preferred. Seed is more preferred.

The electrode constituting the battery of the present invention can be manufactured by forming an active material layer on the current collector.
The current collectors that make up the electrodes include (electrolytic) copper foil, copper mesh (expanded metal), foamed copper, punched copper, copper alloys such as brass, brass foil, brass mesh (expanded metal), foamed brass, punched brass. , Nickel foil, corrosion resistant nickel, nickel mesh (expanded metal), punched 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, Hg, Bi, In, Tl, brass added (electrolytic) copper foil, copper mesh (expanded metal), foamed copper, 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 ・Metal zinc ・Corrosion resistant metal zinc ・Zinc foil ・Zinc mesh (expanded metal) ・(punching) Steel plate ・Nonwoven fabric ・Ni・(Electrolytic) copper foil plated with Zn, Sn, Pb, Hg, Bi, In, Tl, brass, etc. (copper foil), copper mesh (expanded metal), foamed copper, 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, Metal Zinc, Corrosion Resistant Metal Zinc, Zinc Foil, Zinc Mesh (Expanded Metal), (Punching) Steel Plate, Non-woven Fabric Silver; materials used as current collectors and containers for alkaline (storage) batteries and zinc-air batteries.

The electrolytic solution constituting the battery of the present invention is not particularly limited as long as it is usually used as an electrolytic solution of a battery, and examples thereof include a water-containing electrolytic solution and an organic solvent-based electrolytic solution. Liquids are preferred. The water-containing electrolytic solution refers to an electrolytic solution that uses only water as an electrolytic solution raw material (aqueous electrolytic solution) or an electrolytic solution that uses a solution obtained by adding an organic solvent to water as an electrolytic solution raw material. Further, the anion-conductive membrane of the present invention can exhibit anion conductivity even under heating/humidifying conditions. Further, the anion-conductive membrane of the present invention can exhibit anion conductivity even under the condition that the anion-conductive membrane of the present invention or the like is used as a solid electrolyte and no electrolytic solution is present.

As the aqueous electrolytic solution, an alkaline electrolytic solution is preferable. Examples of the alkaline electrolyte 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. The water-based electrolytic solution may be used alone or in combination of two or more.

In addition, the water-containing electrolytic solution may contain an organic solvent used for the organic solvent-based electrolytic solution. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethylsulfoxide, sulfolane, acetonitrile, Examples thereof include benzonitrile, ionic liquids, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like. The organic solvent-based electrolytic solution may be used alone or in combination of two or more. The electrolyte of the organic solvent-based electrolytic solution is not particularly limited, but LiPF ₆ , LiBF ₄ , LiB(CN) ₄ , lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide ( LiTFSI) and the like are preferable.
In the case of a water-containing electrolytic solution containing an organic solvent, the content of water is preferably 10% by mass or more and 99.9% by mass or less, more preferably 20% by mass or more, relative to 100% by mass of the electrolytic solution. It is 99.9 mass% or less.

The anion conductive membrane of the present invention can be used not only as a solid electrolyte but also as an ion exchange membrane. When the anion conductive membrane of the present invention is used as an ion exchange membrane, an electrolyte solution or a gel electrolyte can be separately used as an electrolyte material.
When using a gel electrolyte in the battery of the present invention, the gel electrolyte is not particularly limited as long as it can be used as the electrolyte of the battery, for example, a solid electrolyte containing a compound similar to the above separator, and cross-linking. Examples include gel electrolytes cross-linked with agents.

The form of the battery of the present invention is a primary battery; a chargeable/dischargeable secondary battery (storage battery); a mechanical charge type battery (a battery that mechanically replaces a zinc negative electrode); a third electrode type battery (a negative electrode for charging). A battery using a suitable electrode and an electrode suitable for discharge); a fuel cell or the like may be used, but a secondary battery or a fuel cell is preferable.
The type of the battery of the present invention is not particularly limited, but it is a battery using an alkaline electrolyte such as an alkaline dry battery, a nickel-hydrogen battery, a nickel-cadmium battery, a manganese-zinc battery, a nickel-zinc battery, a fuel battery and an air battery. It is preferable to have.

The anion-conductive membrane of the present invention has selective permeability for hydroxide ions, has sufficiently high mechanical strength, and can effectively suppress the growth of dendrites, thus producing dendrites. It can be preferably used as an electrode active material, especially as a separator of a battery using a zinc species, and can have a long battery life.

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

<Puncture strength test>
The puncture strength was measured as follows according to Japanese Industrial Standard JIS Z 1707 (General rules for plastic film for food packaging).
The test piece was fixed, and a semicircular needle having a diameter of 1.0 mm and a tip shape radius of 0.5 mm was pierced at a speed of 50 mm±5 mm per minute, and the maximum stress until the needle penetrated was measured. The number of test pieces was 5 or more, and the average value was calculated.

<Charge/discharge test>
A charge/discharge test was conducted under the following conditions.
・Number of cells to be charged: 5 cells (show the average value)
・Cell constituent working electrode: Zinc oxide powder/PTFE (polytetrafluoroethylene) mixture adhered to tin-plated punched steel plate collector Counter electrode: Zinc oxide/PTFE mixture, tin-plated punched steel plate welded to zinc metal What was attached to the electric body Reference electrode: Mercury electrode Electrolyte: Zinc oxide-saturated KOH aqueous solution with a concentration of 6.7 mol/L Separator: Anion conductive membrane/charge/discharge conditions Charge/discharge current value: 60 mA/cm ² − 10 min

(Example 1)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (TRD2001, manufactured by JSR, solid content concentration: 48%, alkylbenzene) Sulfonate: trace amount, polycarboxylic acid salt: less than 1% by mass), carboxymethyl cellulose (CMC1380, manufactured by Daicel Finechem) and pure water are kneaded and kneaded at a mass ratio of 100:100:3:20, and rolled. Thus, the thickness was set to 100 μm, and this film was subjected to heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 3.0 N. When the charge and discharge was evaluated, 450 cycles were achieved.

(Example 2)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (JSR0589, manufactured by JSR, solid content concentration: 50%, alkylbenzene Sulfonate: less than 1% by mass), carboxymethyl cellulose (CMC1380, manufactured by Daicel FineChem) and pure water are kneaded and kneaded in a mass ratio of 100:100:3:20, and rolled to a thickness of 100 μm. Then, this membrane was subjected to heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 1.0 N. Further, when charge and discharge evaluation was performed, 410 cycles were achieved.

(Example 3)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 0.20 μm) and an aqueous dispersion of a styrene-butadiene copolymer (JSR0573, manufactured by JSR, solid content concentration: 48%, alkylbenzene) A sulfonate: a trace amount), carboxymethyl cellulose (CMC1380, manufactured by Daicel FineChem) and pure water were kneaded and kneaded at a mass ratio of 100:100:3:20, and rolled to a thickness of 100 μm. Was heated at 80° C. for 1 hour and then at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 1.4N. Further, when charge and discharge evaluation was performed, 440 cycles were achieved.

(Example 4)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 0.20 μm) and an aqueous dispersion of a styrene-butadiene copolymer (JSR0573, manufactured by JSR, solid content concentration: 48%, alkylbenzene) Sulfonate: Trace amount, carboxymethyl cellulose (CMC1380, manufactured by Daicel Finechem), sodium dodecylbenzene sulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and pure water 100:100:3:3.1: The kneader was kneaded in a mass ratio of 19 and roll-rolled to a thickness of 100 μm, and this film was subjected to heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion conductive membrane. ..
The puncture strength of this anion conductive membrane was 1.7 N. Further, when charge and discharge evaluation was performed, 410 cycles were achieved.

(Example 5)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 0.20 μm) and an aqueous dispersion of a styrene-butadiene copolymer (JSR0573, manufactured by JSR, solid content concentration: 48%, alkylbenzene) Sulfonate: Trace amount, carboxymethyl cellulose (CMC1380, manufactured by Daicel Finechem), sodium dodecylbenzene sulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and sodium polyacrylate (Aquaric DL453, manufactured by Nippon Shokubai, solid) 35%) and pure water at a mass ratio of 100:100:3:3.1:1.4:18.6 and kneader-kneaded, and roll-rolled to a thickness of 100 μm. An anion conductive membrane was prepared by performing heat treatment at 1° C. for 1 hour and then at 120° C. for 1 hour.
The puncture strength of this anion conductive membrane was 2.6 N. Further, when charge and discharge evaluation was performed, 430 cycles were achieved.

(Example 6)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (JSR0623A, manufactured by JSR, solid content concentration: 49%, alkylbenzene Sulfonate: less than 0.3% by mass), carboxymethylcellulose (CMC1380, manufactured by Daicel FineChem) and pure water are kneaded and kneaded in a mass ratio of 100:100:3:20, and rolled to obtain a thickness. The film having a thickness of 100 μm was subjected to heat treatment at 80° C. for 1 hour and then at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 1.6N. Moreover, when charge and discharge evaluation was performed, 400 cycles were achieved.

(Example 7)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (TRD102A, manufactured by JSR, solid content concentration: 48%, alkylbenzene Sulfonate: less than 1% by mass, polycarboxylic acid salt: less than 1% by mass), carboxymethylcellulose (CMC1380, manufactured by Daicel Finechem) and pure water at a mass ratio of 100:100:3:20, kneader-kneaded, and roll The film was rolled to have a thickness of 100 μm, and the film was subjected to heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion-conductive film.
The puncture strength of this anion conductive membrane was 3.5N. In addition, when the charge and discharge was evaluated, 480 cycles were achieved.

(Example 8)
Aqueous dispersion of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and styrene-butadiene copolymer (SR-107, manufactured by A&L Japan, solid content concentration: 48) %), carboxymethyl cellulose (CMC1380, manufactured by Daicel Finechem), sodium dodecylbenzene sulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and pure water at a mass ratio of 100:100:3:3.1:19. The kneader was kneaded in, and roll-rolled to a thickness of 100 μm, and this film was heat-treated at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion-conductive membrane.
The puncture strength of this anion conductive membrane was 1.8N. Further, when the charge and discharge was evaluated, 390 cycles were achieved.

(Example 9)
Aqueous dispersion of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter 0.20 μm) and styrene-butadiene copolymer (SR-140, manufactured by A&L Japan, solid content concentration: 48) %), carboxymethyl cellulose (CMC1380, manufactured by Daicel Finechem), sodium dodecylbenzene sulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and pure water at a mass ratio of 100:100:3:3.1:19. The kneader was kneaded in, and roll-rolled to a thickness of 100 μm, and this film was heat-treated at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion-conductive membrane.
The puncture strength of this anion conductive membrane was 2.0 N. Further, when charge and discharge evaluation was performed, 410 cycles were achieved.

(Preparation example 1)
(Preparation of Nonionic Styrene-Butadiene Copolymer)
After charging 0.5 parts by mass of polyoxyethylene lauryl ether and 57 parts by mass of deionized water into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, nitrogen gas was introduced into the flask. Replaced with.
On the other hand, a dropping funnel was charged with 0.5 part by mass of polyoxyethylene lauryl ether, 58 parts by mass of styrene, 40 parts by mass of 1,3-butadiene, 0.5 part by mass of t-dodecyl mercaptan and 38 parts by mass of deionized water. An emulsion was prepared. Then, while gently blowing nitrogen gas into the flask, the temperature was raised to 65° C. under stirring, 6 parts by mass of a 5% ammonium persulfate aqueous solution was added, and then the pre-emulsion obtained above was uniformly stirred for 5 hours. It was dripped in. After the dropping was completed, the dropping funnel was washed with 5 parts by mass of deionized water, and the obtained washing liquid was dropped into the flask. Then, the content in the flask was maintained at 65° C. for 2 hours to complete the polymerization. The obtained reaction liquid was cooled to room temperature to obtain an aqueous dispersion of a conjugated diene-based copolymer having a nonvolatile content of 49 mass% and a volume average particle diameter of 220 nm.
The minimum film-forming temperature in the aqueous dispersion of the obtained conjugated diene-based copolymer was -1°C.

(Example 10)
An aqueous dispersion of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and a styrene-butadiene copolymer synthesized according to Preparation Example 1 and carboxymethyl cellulose (CMC1380, Daicel Finechem). Kneader) and sodium dodecylbenzenesulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and pure water at a mass ratio of 100:100:3:3.1:19, and roll rolling. Then, the thickness was set to 100 μm, and this membrane was subjected to heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 1.5 N. Moreover, when charge and discharge evaluation was performed, 400 cycles were achieved.

(Example 11)
An aqueous dispersion of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and a styrene-butadiene copolymer synthesized according to Preparation Example 1 and carboxymethyl cellulose (CMC1380, Daicel Finechem). Manufactured), sodium dodecylbenzene sulfonate (Neoperex G65, manufactured by Kao, solid content 65%) and pure water at a mass ratio of 100:100:3:0.77:19.7, and kneader-rolled. By doing so, a thickness of 100 μm was obtained, and this film was subjected to a heat treatment at 80° C. for 1 hour and further at 120° C. for 1 hour to prepare an anion conductive membrane.
The puncture strength of this anion conductive membrane was 1.1 N. Moreover, when charge and discharge evaluation was performed, 400 cycles were achieved.

(Comparative Example 1)
An aqueous dispersion of hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and a styrene-butadiene copolymer synthesized according to Preparation Example 1 and carboxymethyl cellulose (CMC1380, Daicel Finechem). Manufactured) and pure water at a mass ratio of 100:100:3:20 and kneader-kneaded, and roll-rolled to a thickness of 100 μm. This film was heated at 80° C. for 1 hour and then at 120° C. for 1 hour. An anion conductive membrane was produced by performing heat treatment.
The puncture strength of this anion conductive film was 0.3N. In addition, when the charge and discharge was evaluated, 200 cycles were achieved.

Claims (7)

Conjugated diene polymers, layered double hydroxides, and the anionic surfactant component seen including,
An anion conductive membrane, which is used as a separator of a secondary battery . The anionic surfactant component has at least one functional group selected from the group consisting of a sulfonic acid (salt) group, a sulfonic acid ester group, and a phosphoric acid (salt) group. Item 1. The anion conductive membrane according to item 1 . The anion conductive membrane according to claim 1 or 2 , wherein the layered double hydroxide is hydrotalcite. The anion conducting membrane 100 mass%, the content of the anionic surfactant component 0.01% by mass or more, according to any one of claims 1 to 3, characterized in that at most 7 mass% Anion conducting membrane. Furthermore, anion-conducting membrane according to any one of claims 1 to 4, characterized in that it comprises an acid group-containing polymer. The separator for a secondary battery characterized in that it is configured to include an anion conducting membrane according to any one of claims 1-5. Secondary battery characterized by being constituted by using a separator for a secondary battery according to claim 6.