Coating material for battery member, electrolyte, battery, and coating agent for battery member

Abstract

A coating material for a battery member contains a polymer having the ability to preferentially conduct metal ions.

Description

Technical Field

[0001] The present disclosure relates to a coating material for a battery member, an electrolyte, a battery, and a coating agent for a battery member. Background Art

[0002] Lithium ion batteries and other batteries that are charged and discharged with the migration of metal ions between the positive electrode and the negative electrode are being actively studied due to their high capacity. As electrolytes for lithium ion batteries, solutions of lithium salts containing organic solvents or ionic liquids are known, and for the sake of safety and processability, research on solid electrolytes is being promoted (Patent Documents 1 and 2 and Non-Patent Document 1). As solid electrolytes, various types of compounds such as oxide-based solid electrolytes and sulfide-based solid electrolytes are known.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Chinese Patent Application No. 112448100

[0006] Patent Document 2: Chinese Patent Application No. 110247111

[0007] Non-patent literature

[0008] Non-patent literature 1: Journal of The Electrochemical Society, 2020, 167, 070559. Summary of the invention

[0009] Problems to be solved by the invention

[0010] Here, components of batteries such as solid electrolytes have the following problems: many components have poor resistance to electrochemical reactions such as oxidation and reduction, and there is a lack of freedom in combining the components.

[0011] The present disclosure is made in view of the above circumstances, and an object thereof is to provide a coating material that can improve the electrochemical resistance of a battery member. Another object of the present disclosure is to provide an electrolyte or a battery including such a coating material, and a coating agent for a battery member that can form such a coating material.

[0012] Means used to solve problems

[0013] The present disclosure includes the following embodiments [1] to

[13] .

[0014] [1] A coating material for a battery member, comprising a polymer having the ability to preferentially conduct metal ions.

[0015] [2] The coating material for a battery member according to [1], which is used for coating an ion-conductive inorganic solid electrolyte.

[0016] [3] The coating material for a battery member according to [2], wherein the ion conductive inorganic solid electrolyte has a Li / Li + The reaction occurs in the potential range of -0.1 to 4.5 V.

[0017] [4] The battery member coating material according to [2] or [3], wherein the ion-conductive inorganic solid electrolyte is in the form of particles.

[0018] [5] The battery member coating material according to any one of [2] to [4], wherein the ion-conductive inorganic solid electrolyte is in a sheet form.

[0019] [6] The battery member coating material according to any one of [1] to [3], further comprising a swelling agent.

[0020] [7] The battery member coating material according to 6], wherein the swelling agent is at least one of an organic solvent and an ionic liquid.

[0021] [8] The battery member coating material according to any one of [1] to [7], wherein the polymer has at least one of an anionic functional group having a metal ion as a counter cation and a functional group having an anion capturing ability.

[0022] [9] The coating material for a battery member according to any one of [1] to [8], wherein the coating material has a Li / Li + The potential range of -0.1 to 4.5 V is stabilized.

[0023]

[10] An electrolyte comprising the battery member coating material according to any one of [1] to [9].

[0024]

[11] A coated electrolyte comprising an electrolyte and a battery component coating material covering at least a portion of a surface of the electrolyte, wherein the battery component coating material contains a polymer having an ability to preferentially conduct metal ions.

[0025]

[12] A battery comprising the battery member coating material according to any one of [1] to [9], and the electrolyte according to

[10] or the coated electrolyte according to

[11] .

[0026]

[13] A coating agent for a battery member, comprising a polymer having the ability to preferentially conduct metal ions.

[0027] Effects of the Invention

[0028] According to the present disclosure, it is possible to provide a coating material that can improve the electrochemical resistance of a battery member. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Example 1.

[0030] Figure 2 This is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Comparative Example 1.

[0031] Figure 3 This is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Example 2.

[0032] Figure 4 This is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Example 3. DETAILED DESCRIPTION

[0033] The battery member coating material of the present embodiment includes a polymer having an ability to preferentially conduct metal ions. The battery member coating material of the present embodiment can be formed of a battery member coating agent including a polymer having an ability to preferentially conduct metal ions.

[0034] The battery component coating material of this embodiment can improve the electrochemical resistance of the battery component. Therefore, for example, it can be applied to the electrolyte of the battery. More specifically, by coating the surface of the ion-conductive inorganic solid electrolyte contained in the electrolyte with the battery component coating material, the electrochemical resistance of the ion-conductive inorganic solid electrolyte can be improved.

[0035] The battery member coating material may cover the surface of each particle of the ion-conductive inorganic solid electrolyte contained in the electrolyte, or may cover the surface of the electrolyte formed into a shape such as a sheet or a cylinder.

[0036] The battery component coating agent of the present embodiment may contain an ion conductive inorganic solid electrolyte, a swelling agent, etc. as optional components in addition to the polymer having the ability to preferentially conduct metal ions. When the ion conductive inorganic solid electrolyte is contained in the battery component coating agent, the particles of the ion conductive inorganic solid electrolyte are contained in the form of being dispersed in the battery component coating agent, so that the particles of the ion conductive inorganic solid electrolyte can be coated with the battery component coating agent in advance, and can be used as an electrolyte composition for forming an electrolyte.

[0037] [Polymer having the ability to preferentially conduct metal ions]

[0038] As a polymer having the ability to preferentially conduct metal ions (hereinafter also referred to as a polymer), for example, when the migration number of metal ions is measured at room temperature (25°C) for at least one of the following compositions (A) and (B), the polymer may have a migration number of metal ions of 0.4 or more, 0.5 or more, 0.6 or more, or 0.7 or more.

[0039] (A) A composition comprising 33% by mass of the polymer and 67% by mass of a nonionic plasticizer

[0040] (B) A composition comprising 31.9 mass % of the polymer and the remaining total amount of a metal salt and a nonionic plasticizer and having a metal ion concentration of 0.3 mol / L

[0041] It can be a polymer that reaches 0.4 or more, 0.5 or more, 0.6 or more, or 0.7 or more when the migration number of metal ions is measured for a composition containing 33% by mass of the polymer and a metal ion concentration of 1.0 mol / l, or a composition containing 31.9% by mass of the polymer and 4.3% by mass of a metal salt and a metal ion concentration of 0.71 mol / l. With regard to the metal ions contained in the composition, when the polymer has an anionic functional group, it can be a counter cation of the anionic functional group, or a substance added as a metal salt. The polymer having the ability to preferentially conduct metal ions can be a polymer having the ability to preferentially conduct alkali metal ions. As a nonionic plasticizer, at least one of other resins such as an organic solvent and a fluorine-based resin can be listed. The organic solvent can be an aprotic solvent. The aprotic solvent can be at least one selected from the group consisting of a carbonate-based solvent, a fluorine-based solvent, and an ether-based solvent. As a fluorine-based resin, it is preferably a resin having a carbon chain as a main chain. The carbon chain can be formed by free radical polymerization of ethylenically unsaturated groups. The fluorine-based resin may be poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP).

[0042] Specific examples of the organic solvent include specific examples of the organic solvent contained in the electrolyte composition described below. The organic solvent may be a mixed solvent containing ethylene carbonate and propylene carbonate at a volume ratio of 1:1.

[0043] The concentration of metal ions can be adjusted by adding metal salts. For example, when the metal salt is an alkali metal salt, the alkali metal salt is not particularly limited, and the alkali metal is denoted as M, and examples thereof include MF, MCl, MBr, MI, MClO4, MPF6, MBF4, M2SO4, M[(C h F 2h+1 )SO3](h is 0~3), M[(C h F 2h+1)SO2]2N (h is 0 to 3), etc. When the polymer has the structural unit (A), M may be the same alkali metal element as the alkali metal element contained in the structural unit (A).

[0044] The polymer having the ability to preferentially conduct metal ions can be listed as a polymer containing at least one of an anionic functional group having a metal ion as a counter cation (also referred to as functional group (A)) and a functional group having an anion capture ability (also referred to as functional group (B). The structure of the polymer is not particularly limited, and a structure having a carbon chain as a main chain can be listed, and the carbon chain can be formed by free radical addition polymerization of a monomer having an ethylenically unsaturated group.

[0045] The metal ion as the counter cation of the functional group (A) can be at least one of an alkali metal ion and an alkaline earth metal ion, or an alkali metal ion. As the alkali metal ion, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, etc. can be listed, which can be lithium ion, sodium ion or potassium ion, or lithium ion or sodium ion, or lithium ion. Hereinafter, the structural unit comprising the functional group (A) and the metal ion as the counter cation of the functional group (A) is also referred to as structural unit (A). The structural unit (A) can have a structure obtained by free radical addition polymerization of a monomer having an ethylenically unsaturated group. The metal ion as the counter cation of the functional group (A) can be an alkali metal ion identical to the alkali metal ion contained in the ion-conductive inorganic solid electrolyte.

[0046] The structural unit (A) may have at least one selected from the group consisting of a conjugated anion of a sulfonyl imide group, a conjugated anion of a sulfonic acid group, and a conjugated anion of a phenolic hydroxyl group as the functional group (A). The conjugated anion of a sulfonyl imide group, the conjugated anion of a sulfonic acid group, and the conjugated anion of a phenolic hydroxyl group may be included in the group having a conjugated anion of a sulfonyl imide group, the group having a conjugated anion of a sulfonic acid group (sulfonate group), and the group having a conjugated anion of a phenolic hydroxyl group described below.

[0047] The group having a sulfonimide group may be included in the structural unit (A) represented by the following formula (A1).

[0048] [Chemical formula 1]

[0049]

[0050] (In formula (A1), X is a divalent organic group having 1 to 20 carbon atoms, Y is a halogen atom or a monovalent organic group having 1 to 20 carbon atoms, and M + is an alkali metal ion, and * indicates the position where the structural unit (A1) is bonded to other structural units.

[0051] As X, there is no particular limitation, and it can be a hydrocarbon group, a group having a heteroatom, or a heterocycle. As X, more specifically, there can be listed divalent groups such as hydrocarbon groups, groups having a chemical structure in which one or more carbon atoms (methylene) of a hydrocarbon group are replaced by a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-. It should be noted that when there are multiple connecting groups, these connecting groups are not adjacent to each other. In addition, the above-mentioned divalent group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As a substituent, it can be a univalent substituent, for example, a halogen atom can be listed. As the above-mentioned hydrocarbon group, there is no particular limitation, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As an aliphatic hydrocarbon group, it can be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group and a cyclic hydrocarbon group. In addition, the hydrocarbon group can be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group. X may be bonded to one or both of the nitrogen atom of the maleimide group and the sulfur atom of the sulfonyl group via a carbon atom of X.

[0052] The number of carbon atoms possessed by X may be 1 to 15, 2 to 10, or 3 to 8. X may be a group having an aromatic ring, or a group having an aromatic carbocyclic ring such as a benzene ring. Substituents such as an alkyl group, a halogen atom, or an electron-withdrawing group may be bonded to the carbon atom that is a ring member of the carbocyclic ring. The hydrocarbon group as X is preferably a phenylene group, an alkylene group having 1 to 8 carbon atoms, a polyoxyalkylene group, or a group in which a part or all of the hydrogen atoms bonded to the carbon atoms they possess are replaced by halogen atoms such as fluorine atoms, and more preferably a phenylene group or a substituted phenylene group substituted by an alkyl group, a halogen atom, an electron-withdrawing group, or the like. As the electron-withdrawing group, halogen atoms, sulfonic acid groups or their salts, sulfonic acid esters, nitro groups, nitrile groups, etc. may be listed.

[0053] In formula (A1), when Y is a monovalent organic group, the organic group is not particularly limited and may be a hydrocarbon group, a group having a heteroatom, or a heterocycle. More specifically, as Y, a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene) of a hydrocarbon group are replaced by a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, etc. may be listed. It should be noted that when there are multiple connecting groups, the connecting groups are not adjacent to each other. In addition, the above-mentioned monovalent group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As a substituent, a monovalent substituent may be listed, for example, a halogen atom may be listed. As the above-mentioned hydrocarbon group, there is no particular limitation and it may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As an aliphatic hydrocarbon group, it may be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group.

[0054] The number of carbon atoms possessed by Y may be 1 to 15, 1 to 10, 1 to 8, 1 to 5, or 1 to 3. The hydrocarbon group as Y is preferably a phenyl group, an alkyl group having 1 to 5 carbon atoms, or a group in which a part or all of the hydrogen atoms bonded to the carbon atoms possessed by these groups are substituted by halogen atoms such as fluorine atoms, more preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and further preferably a fluorinated alkyl group having 1 to 3 carbon atoms such as a trifluoromethyl group. The fluorinated alkyl group may be a perfluoroalkyl group. When Y is a halogen atom, the halogen atom is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.

[0055] In formula (A1), M + is an alkali metal ion, preferably a lithium ion (Li + ), sodium ion (Na + ) or potassium ion (K + ), more preferably lithium ion. + Can contain Li + 、Na + and K + The two or three ions in the mixture preferably substantially only contain a single ion.

[0056] The group having a conjugated anion of a phenolic hydroxyl group is a group having a group obtained by alkali metalizing a hydroxyl group directly bonded to an aromatic ring (ie, a phenolic hydroxyl group (-OH)) (ie, a -OM group in which M is an alkali metal).

[0057] The structural unit (A) may be a group represented by the following formula (A2).

[0058] [Chemical formula 2]

[0059]

[0060] (In formula (A2), Y 2 R is a group having an alkali-metallated phenolic hydroxyl group or a group having a conjugated anion of a sulfonic acid, and * represents the bonding position between the structural unit (A2) and other structural units. 15 ~R 17 are each independently a hydrogen atom or a monovalent substituent, or R 16 is a hydrogen atom or a monovalent substituent, R 15 and R 17 Together they form a divalent substituent. )

[0061] R 15 ~R 17 One or more atoms may be hydrogen atoms, or all of them may be hydrogen atoms.

[0062] In R 15 ~R17 In the case of a monovalent substituent, the monovalent substituent may be a monovalent organic group. The number of carbon atoms in the organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, monovalent substituents such as hydrocarbon groups, groups having a chemical structure formed by replacing one or more carbon atoms (methylene) of the hydrocarbon group with a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring may be cited. In addition, the above-mentioned monovalent substituent may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As a substituent, for example, a halogen atom may be cited. The above-mentioned hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As an aliphatic hydrocarbon group, it may be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a phenyl group.

[0063] About R 15 ~R 17 The monovalent substituent may have an electron withdrawing group or may be the electron withdrawing group itself. The electron withdrawing group may be bonded to the above-mentioned monovalent organic group or the above-mentioned monovalent organic group may be an electron withdrawing group. Examples of the electron withdrawing group include halogen atoms, sulfonic acid groups or their salts, sulfonic acid esters, nitro groups, nitrile groups, etc. Examples of the halogen atom include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0064] In R 15 and R 17 When a divalent organic group is formed together, the number of carbon atoms possessed by the divalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, a hydrocarbon group, a group having a chemical structure formed by replacing one or more carbon atoms (methylene) of the hydrocarbon group with a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, a group having a heterocyclic ring, etc. can be listed. In addition, the above-mentioned divalent organic group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As a substituent, for example, a halogen atom can be listed. The above-mentioned hydrocarbon group is not particularly limited, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As an aliphatic hydrocarbon group, it can be any of a straight-chain hydrocarbon group, a branched hydrocarbon group and a cyclic hydrocarbon group. In addition, the hydrocarbon group can be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. As a hydrocarbon group, a propylene group, a butylene group, etc. can be listed.

[0065] In Y 2 In the case of a group having a phenolic hydroxyl group, Y2 The group may be a group represented by any of the following chemical formulae (A21) to (A26).

[0066] [Chemical formula 3]

[0067]

[0068] (In formula (A21), R A At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which may be Li, Na or K. In formula (A22), R B At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which may be Li, Na or K. In formula (A23), R C At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which may be Li, Na or K. In formula (A24), R D At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which may be Li, Na or K. In formula (A25), R E At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which may be Li, Na or K. In formula (A26), R F At least one of the groups is a -OM group, and the rest are hydrogen atoms or monovalent substituents, and M is an alkali metal element, which can be Li, Na or K.

[0069] When the polymer has a functional group of formula (A21), a -OM group may be bonded to the benzene ring of formula (A21) at the para position from the bonding site of the functional group of formula (A21) and the polymer. A3 The group may be an -OA group. A hydrogen atom, an -OA group, a methyl group, an ethyl group, or a monovalent organic group having 1 to 20 carbon atoms may be bonded to the meta position or the ortho and meta positions independently of the above-mentioned bonding site (wherein, when the monovalent organic group is a saturated hydrocarbon group, it is a methyl group, an ethyl group, or a group having 6 to 20 or 6 to 15 carbon atoms; and when the monovalent organic group is an alkoxy group, it is a group having 4 to 20 or 4 to 15 carbon atoms.).

[0070] The groups represented by formulae (A21) to (A26) may have 1 to 3 -OM groups, 1 or 2 -OM groups, or 1 -OM group.

[0071] In formulae (A21) to (A26), the monovalent substituent is preferably an electron withdrawing group. Examples of the electron withdrawing group include a halogen atom, a sulfonic acid group or a salt thereof, a sulfonic acid ester, a nitro group, and a nitrile group. The halogen atom may be any one of F, Cl, Br, and I.

[0072] In addition, in formulas (A21) to (A26), the monovalent substituent may be an organic group having 1 to 20 carbon atoms. The number of carbon atoms possessed by the organic group may be 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, monovalent groups such as hydrocarbon groups, groups having a chemical structure formed by replacing one or more carbon atoms (methylene) of the hydrocarbon group with a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring may be listed. In addition, the above-mentioned monovalent group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As the substituent, for example, a halogen atom may be listed. The above-mentioned hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it may be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a phenyl group. The monovalent organic group may itself be an electron withdrawing group.

[0073] In Y 2 In the case of a group having a conjugated anion of a sulfonic acid, Y 2 , and examples thereof include groups represented by the following formula (A3).

[0074] [Chemical formula 4]

[0075]

[0076] (In formula (A3), R 19 is a covalent bond or a divalent organic group. M is an alkali metal element, which can be Li, Na or K. )

[0077] In formula (A3), the number of carbon atoms possessed by the divalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, there may be listed divalent substituents such as hydrocarbon groups, groups having a chemical structure in which one or more carbon atoms (methylene) of the hydrocarbon group are substituted by a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring. In addition, the above-mentioned divalent organic group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As the substituent, for example, a halogen atom may be listed. The above-mentioned hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it may be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group. As the hydrocarbon group, methylene, phenylene, etc. may be listed.

[0078] Examples of the group having a conjugated anion of sulfonic acid include -SO3M, -CH2-SO3M, and -C6H4-SO3M.

[0079] Functional group (B) is a functional group having a function as an anion receptor. Anion receptor refers to a chemical species that captures anions by forming electrostatic interactions, hydrogen bonds, acid-base complexes, etc. with anions. Functional group (B) captures the counter anion of the metal ion in the metal salt, promotes the dissociation of the counter anion and the metal ion. Thus, the mobility of the metal ion is increased. In addition, since the counter anion is captured by the polymer via the structural unit (B), the mobility of the counter anion is reduced. It is believed that the migration number of the metal ion is improved as a result. In addition, since the mobility of the metal ion increases, there is a tendency that the conductivity of the metal ion is also improved.

[0080] The low molecular chemical species (compound etc.) that known as anion receptor performs function, as this material, for example, can enumerate the compound of record in U.S. Patent No. 6022643 specification, U.S. Patent No. 5705689 specification, U.S. Patent No. 6120941 specification etc. Functional group (B) has the structure corresponding to the chemical species that performs function as anion receptor. Because this functional group is fixed on polymer, therefore different from existing low molecular anion receptor, the negatively charged ion that is caught can be fixed on the structure of polymer. Therefore, it is believed that it can more effectively suppress the electric current that its participation in the migration of this negatively charged ion is produced.

[0081] It should be noted that the counter anion of the alkali metal salt does not need to be a completely ionized free anion when captured by the functional group, and can be captured by interacting with the functional group in a state of forming an ionic bond or an ion pair with the metal ion.

[0082] The functional group having the function as an anion receptor may be Lewis acidic. In this case, the functional group can capture anions by accepting the non-shared electron pair of anions and forming an acid-base complex. As such functional groups, functional groups with electron-deficient atoms may be listed. It should be noted that electron-deficient atoms refer to atoms that have been covalently bonded to other atoms but whose outermost electrons do not form an octet. As electron-deficient atoms, atoms belonging to the 13th group of the periodic table may be listed, more specifically, at least one of aluminum and boron, or boron.

[0083] In addition, as a functional group having a function as an anion receptor, a group having an azaether moiety may be used. The group having an azaether moiety is a group having an azaether compound as a substituent, wherein the azaether compound is obtained by replacing -O- of an ether compound with -NR E -(Here, R E The azaether moiety may be any one of a chain azaether moiety and a cyclic azaether moiety, and may have both a chain azaether moiety and a cyclic azaether moiety. The group having the azaether moiety may have an electron withdrawing group in, for example, a hydrocarbon moiety.

[0084] The functional group (B) may be included in, for example, a structural unit (B) represented by the following formula (B).

[0085] [Chemical formula 5]

[0086]

[0087] (In formula (B), W is a functional group having a function as an anion receptor, R 1 ~R 3 are each independently a hydrogen atom or a monovalent substituent, or R 3 is a hydrogen atom or a monovalent substituent, R 1 and R 2 Together they form a divalent organic group. * indicates the position where the structural unit (B) is bonded to other structural units.

[0088] The polymer having an ability to preferentially conduct metal ions may contain one or two or more structural units represented by formula (B).

[0089] R 1 ~R 3 One or more of them may be hydrogen atoms, or all of them may be hydrogen atoms. W may be a group represented by formula (B1) described later.

[0090] In R 1 ~R 3In the case of a monovalent substituent, the monovalent substituent may be a monovalent organic group. The number of carbon atoms in the organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, monovalent substituents such as hydrocarbon groups, groups having a chemical structure formed by replacing one or more carbon atoms (methylene) of the hydrocarbon group with a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring may be cited. In addition, the above-mentioned monovalent substituent may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As a substituent, for example, a halogen atom may be cited. The above-mentioned hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As an aliphatic hydrocarbon group, it may be any one of a straight-chain hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any one of a saturated hydrocarbon group and an unsaturated hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a phenyl group.

[0091] It should be noted that, in the present specification, an aromatic hydrocarbon group is a group including an aromatic part and may have an aliphatic part. In addition, in the present specification, a cyclic hydrocarbon group is a group including a cyclic hydrocarbon part and may include a linear or branched hydrocarbon part.

[0092] The monovalent substituent may have an electron withdrawing group, or may be the electron withdrawing group itself. The electron withdrawing group may be bonded to the above-mentioned monovalent organic group, or the above-mentioned monovalent organic group may be an electron withdrawing group. As the electron withdrawing group, a halogen atom, a sulfonic acid group or its salt, a sulfonic acid ester, a nitro group, a nitrile group, etc. may be listed. As the halogen atom, any one of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom may be mentioned.

[0093] In R 1 and R 2 When forming a divalent organic group together, the number of carbon atoms possessed by the divalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. As the organic group, there can be listed divalent substituents such as hydrocarbon groups, groups having a chemical structure formed by replacing one or more carbon atoms (methylene) of the hydrocarbon group with a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring. In addition, the above-mentioned divalent organic group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As the substituent, for example, a halogen atom can be listed. The above-mentioned hydrocarbon group is not particularly limited, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it can be any of a straight-chain hydrocarbon group, a branched hydrocarbon group and a cyclic hydrocarbon group. In addition, the hydrocarbon group can be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. As the hydrocarbon group, propylene and butylene can be listed.

[0094] W preferably has a group represented by the following formula (B1).

[0095] [Chemical formula 6]

[0096]

[0097] (In formula (B1), W B is an atom belonging to Group 13 of the periodic table, R 5 is a covalent bond or a divalent organic group, R 6 and R 7 is a hydrogen atom, an -OH group, a halogen atom or a monovalent organic group, or together forms a divalent organic group. 6 and R 7 They can be the same group or different groups.)

[0098] W B At least one of aluminum and boron may be used, or boron may be used.

[0099] In R 5 In the case of a divalent organic group, the number of carbon atoms possessed by the divalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. Examples of the organic group include monovalent substituents such as a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene) of the hydrocarbon group are substituted by a connecting group such as -O-, -S-, -C(=O)- or -C(=O)O-, and a group having a heterocyclic ring. In addition, the above-mentioned divalent organic group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. The substituent may be an electron-withdrawing group. Examples of the electron-withdrawing group include a halogen atom, a sulfonic acid group or a salt thereof, a sulfonic acid ester, a nitro group, a nitrile group, and the like. As the halogen atom, it may be any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 5 It may be a hydrocarbon group, a halogen-substituted hydrocarbon group, or a hydrocarbon group or a halogen-substituted hydrocarbon group connected to W by an ether bond. B The halogen-substituted hydrocarbon group may be a group in which a part or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms, or may be a partially fluorine-substituted hydrocarbon group or a fully fluorine-substituted hydrocarbon group. 5 It can also be a covalent bond.

[0100] In R 6 or R 7 In the case of a halogen atom, it may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0101] In R 6 or R 7In the case of a monovalent organic group, the number of carbon atoms possessed by the monovalent organic group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. Examples of the organic group include hydrocarbon groups, groups having a chemical structure in which one or more carbon atoms (methylene) of the hydrocarbon group are substituted by a connecting group such as -O-, -S-, -C(=O)- or -C(=O)O-, and groups having a heterocyclic ring. In addition, the above-mentioned monovalent organic group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. The substituent may be an electron-withdrawing group. Examples of the electron-withdrawing group include halogen atoms, sulfonic acid groups or salts thereof, sulfonic acid esters, nitro groups, nitrile groups, and the like. As the halogen atom, it may be any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 6 or R 7 It may be a hydrocarbon group, a halogen-substituted hydrocarbon group, or a hydrocarbon group or a halogen-substituted hydrocarbon group connected to W by an ether bond. B The halogen-substituted hydrocarbon group may be a group in which a part or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms, or may be a partially fluorine-substituted hydrocarbon group or a fully fluorine-substituted hydrocarbon group.

[0102] W may be a group represented by the following formula (B1a) or a group represented by the following formula (B1b).

[0103] [Chemical formula 7]

[0104]

[0105] (In formula (B1a), X 1 and X 2 Each is an oxygen atom (ether bond) or a covalent bond, R 11 and R 12 Each of them is a halogen atom, a monovalent hydrocarbon group, a hydrogen atom or a monovalent halogen-substituted hydrocarbon group, and may be a halogen atom (except when X is an oxygen atom), a monovalent hydrocarbon group or a monovalent halogen-substituted hydrocarbon group, or R 11 and R 12 At least one of them is a monovalent hydrocarbon group or a monovalent halogen-substituted hydrocarbon group. 11 and R 12 They can be the same group or different groups.)

[0106] [Chemical formula 8]

[0107]

[0108] (In formula (B1b), X 3 and X 4 Each is an oxygen atom (ether bond) or a covalent bond, R 13 is a divalent hydrocarbon group or a divalent halogen-substituted hydrocarbon group.)

[0109] In formula (B1a), R 11 When X is a halogen atom, 1 Can be a covalent bond, in R 12 When X is a halogen atom, 2 It can be a covalent bond. 11 or R 12 In the case of a monovalent hydrocarbon group or a monovalent halogen-substituted hydrocarbon group, the number of carbon atoms possessed by the monovalent hydrocarbon group or the monovalent halogen-substituted hydrocarbon group may be 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 1 to 3. The halogen-substituted hydrocarbon group may be a group obtained by replacing a part or all of the hydrogen atoms possessed by the hydrocarbon group with halogen atoms, or may be a partially fluorinated hydrocarbon group or a fully fluorinated hydrocarbon group.

[0110] R 11 and R 12 Each independently represents -F, -CH3, -C2H5, -C3H7, -C6H5 (phenyl), -C6H n F 5-n (n is an integer of 0 to 4, and may be an integer of 0 to 3.), -CF3, -CH2CF3, -CH2CF3F7, -CH(CF3)2, -C(CF3)2-C6H5, -C(CF3)3, -C6H n (CF3) 5-n (n is an integer from 0 to 4, and may be 1 or 2.)

[0111] In formula (B1b), the number of carbon atoms possessed by the divalent hydrocarbon group or the divalent halogen-substituted hydrocarbon group may be 1 to 20, 1 to 15, 2 to 10, or 3 to 8. The halogen-substituted hydrocarbon group may be a group obtained by replacing a part or all of the hydrogen atoms possessed by the hydrocarbon group with halogen atoms, or may be a partially fluorinated hydrocarbon group or a fully fluorinated hydrocarbon group.

[0112] R 13 Examples include -C2H4-, -C3H6-, -C4H8-, -C5H 10 -、-C6H 12 -、-C7H 14 -、-C8H 16 -、-C9H 18 -、-C 10 H 20 -, etc., groups obtained by replacing part or all of their hydrogen atoms with fluorine, etc. More specifically, -C(CH3)2-C(CH3)2- is preferred.

[0113] The molar ratio m of the structural unit (B) to all structural units contained in the polymer may be 0.2 to 0.8, 0.25 to 0.75, 0.3 to 0.7, 0.35 to 0.65, or 0.4 to 0.6.

[0114] The molar ratio n of the structural unit (A) to all structural units contained in the polymer may be 0.25 to 0.75, 0.3 to 0.7, 0.35 to 0.65, or 0.4 to 0.6.

[0115] There is no problem if the sum of m and n is 1 or less, and may be 0.95 or less. In addition, the sum of m and n may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more.

[0116] The content of the structural unit (A) may be 5 to 90% by mass, 20 to 80% by mass, 40 to 75% by mass, or 55 to 70% by mass based on the total mass of the polymer.

[0117] The content of the structural unit (B) relative to the total mass of the polymer may be greater than 10% by mass and less than 95% by mass, or may be 15 to 95% by mass, or 20 to 95% by mass, or 20 to 80% by mass, or 25 to 60% by mass, or 30 to 45% by mass.

[0118] The total content of the structural unit (A) and the structural unit (B) may be 50% by mass or more, 70% by mass or more, 90% by mass or more, or 95% by mass or more relative to the total mass of the polymer.

[0119] The polymer may contain a structural unit different from either the structural unit (A) or the structural unit (B), that is, a structural unit (C). Examples of the structural unit (C) include the structural unit represented by the following structural unit (C1) and the structural unit represented by the following structural unit (C2).

[0120] [Chemical formula 9]

[0121]

[0122] (In formula (C1), R 21 ~R 24 Each is independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. * indicates the position where the structural unit (C1) is bonded to another structural unit. )

[0123] [Chemical formula 10]

[0124]

[0125] (In formula (C2), R 25 is a divalent organic group having 1 to 20 carbon atoms, R 26 and R 27 Each is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms. 25 It can form a ring having an ethylene unit of formula (C2) and an imide group (succinimide ring or its N-derivative) or a ring having an acid anhydride group (succinic anhydride ring).

[0126] R 21 ~R 24 One or more of the 1 ... 1 -R 29 The group shown. 21 ~R 24 The number of carbon atoms each has may be 1 to 40, 1 to 20, 2 to 15, or 4 to 13. 1 is a divalent linking group, for example, a covalent bond, -O-, -S-, -C(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)NR 38 -or-NR 39 C(=O)-. 1 In the case of a covalent bond, -O-, -S-, -C(=O)-, -C(=O)O- or -OC(=O)-, R 29 is a hydrogen atom or a monovalent organic group. 38 -In the case of R 29 , R 38 Each is a hydrogen atom or a monovalent organic group, or R 29 With R 38 Together they form a ring. 39 In the case of C(=O)-, R 29 and R 39 are each independently a hydrogen atom or a monovalent organic group, or R 29 With R 39 Together they form a ring. As R 29 , R 38 and R 39 The monovalent organic group of R may have 1 to 20 or 1 to 10 organic groups. 38 When Z is a monovalent organic group, it may be a monovalent hydrocarbon group having 1 to 20 carbon atoms. 1In the case of a covalent bond or -C(=O)O-, R 29 It may be a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. 1 is a covalent bond and R 29 When it is a hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group. 29 It may be a monovalent organic group other than a hydrocarbon group or a hydrocarbon group having a ring structure. 1 When it is -O-, it may be a monovalent organic group other than the group represented by WH when W is an alkyl ether. 26 ~R 28 When it is a monovalent organic group, examples of the monovalent organic group include the following: 25 The same groups as those listed in the examples.

[0127] In addition, the structural unit (C) may include a structural unit that is a precursor of the structural unit (A) (also referred to as a structural unit (Ap). Such structural units include unreacted structural units that cannot be converted into the structural unit (A) among the structural units that are precursors of the structural unit (A) (for example, structural units derived from the monomer (A2') described later), and intermediate structural units, for example, groups that are conjugate acids of the structural unit (A) (i.e., groups that replace the alkali metal ions that are the counter cations of the structural unit (A) with H + The counter cation contained in the structural unit (Ap) can be NH4 + , organic ammonium cations, metal ions such as alkaline earth metal ions, etc. The polymer may contain 85 mol % or more, 90 mol % or more, or 95 mol % or more of the structural unit (A) relative to the total amount of the structural unit (A) and the structural unit (Ap).

[0128] The polymer may include a structural unit derived from a hydrocarbon compound having a plurality of ethylenically unsaturated groups, such as butadiene and isoprene.

[0129] The polymer may have a structural unit derived from a crosslinking agent. Examples of the crosslinking agent include compounds having a plurality of ethylenically unsaturated groups in the molecule, such as hexanediol diacrylate, pentaerythritol tetraacrylate, divinylbenzene, and triethylene glycol divinyl ether.

[0130] The number average molecular weight (Mn) of the polymer may be 5,000 to 200,000, 8,000 to 120,000, or 10,000 to 100,000. The weight average molecular weight (Mw) of the polymer may be 5,000 to 300,000, 10,000 to 250,000, or 20,000 to 100,000. The molecular weight distribution (Mw / Mn) of the polymer may be 1.0 to 3.5, or 1.3 to 2.7. The number average molecular weight and weight average molecular weight of the polymer may be measured, for example, by gel permeation chromatography.

[0131] Relative to the total amount of the coating agent for battery components, the content of the polymer in the coating agent for battery components may be 4% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more. In addition, relative to the total amount of the coating agent for battery components, the content of the polymer in the coating agent for battery components may be 90% by mass or less, 80% by mass or less, 60% by mass or less, or 50% by mass or less. Relative to the total amount of the coating agent for battery components, the content of the polymer in the coating agent for battery components may be 4% by volume or more, 10% by volume or more, 20% by volume or more, or 30% by volume or more. In addition, relative to the total amount of the coating agent for battery components, the content of the polymer in the coating agent for battery components may be 90% by volume or less, 80% by volume or less, 60% by volume or less, or 50% by volume or less.

[0132] In addition, for example, when the coating agent for battery components includes an ion-conductive inorganic solid electrolyte, the content of the polymer in the coating agent for battery components may be 1 to 30% by mass, 2 to 25% by mass, or 4 to 20% by mass relative to the total amount of the coating agent for battery components. In addition, for example, when the coating agent for battery components includes an ion-conductive inorganic solid electrolyte, the content of the polymer in the coating agent for battery components may be 1 to 50% by volume, 5 to 40% by volume, or 10 to 35% by volume.

[0133] The coating agent for battery components may contain a metal salt in addition to the above-mentioned polymer. The metal salt may be at least one of an alkali metal salt and an alkaline earth metal salt, or may be an alkali metal salt. The alkali metal salt is not particularly limited, and the alkali metal is denoted as M, and examples thereof include MF, MCl, MBr, MI, MClO4, MPF6, MBF4, M2SO4, M[(C h F 2h+1 )SO3](h is 0~3), M[(C h F 2h+1)SO2]2N (h is 0 to 3), etc. In the case where the polymer has a structural unit (A), M may be the same alkali metal element as the alkali metal element possessed by the structural unit (A). M may be lithium, sodium or potassium, or lithium. In addition, in the case where the polymer has a functional group (B), the coating agent for battery components may contain an alkali metal salt.

[0134] The coating agent for battery components can be made into a composite further comprising other resins such as fluorine resins, fabrics such as non-woven fabrics, porous materials, viscosity adjusting materials, etc. As other resins, fluorine resins can be listed. As fluorine resins, it is preferably a resin having a carbon chain as a main chain. The carbon chain can be formed by free radical polymerization of ethylenically unsaturated groups. As fluororesins, poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (PVDF), etc. can be listed. Relative to the total amount of the coating agent for battery components, the content of other resins in the coating agent for battery components can be 30% by mass or less, or 0.1 to 20% by mass, or 1 to 15% by mass, or 1 to 10% by mass. In addition, relative to 100 parts by mass of polymers, the content of other resins in the coating agent for battery components or the coating material for battery components can be 1 to 200 parts by mass, or 3 to 100 parts by mass, or 5 to 80 parts by mass, or 10 to 60 parts by mass.

[0135] The total amount of the ion-conductive inorganic solid electrolyte, the polymer having the ability to preferentially conduct metal ions, and the swelling agent in the coating agent for battery components may be 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99.9% by mass or less, or 99% by mass or less, relative to the total amount of the coating agent for battery components. In addition, the total amount of the ion-conductive inorganic solid electrolyte, the polymer having the ability to preferentially conduct metal ions, and the swelling agent in the coating agent for battery components may be 70 to 99.9% by mass, or 80 to 99% by mass, relative to the total amount of the coating agent for battery components.

[0136] The total amount of the ion-conductive inorganic solid electrolyte, the polymer having the ability to preferentially conduct metal ions, and the swelling agent in the coating agent for battery components may be 70% by volume or more, 80% by volume or more, 90% by volume or more, 95% by volume or more, 97% by volume or more, 99.9% by volume or less, or 99% by volume or less, relative to the total amount of the coating agent for battery components. In addition, the total amount of the ion-conductive inorganic solid electrolyte, the polymer having the ability to preferentially conduct metal ions, and the swelling agent in the coating agent for battery components may be 70 to 99.9% by volume, or 80 to 99% by volume, relative to the total amount of the coating agent for battery components.

[0137] The method for producing the polymer is not particularly limited, and examples thereof include a method of polymerizing a monomer (monomer mixture) comprising at least one of the following monomers: a monomer having an anionic functional group ionized by an alkali metal or a monomer having a precursor of the anionic functional group (hereinafter referred to as monomer (A').), and a monomer (B') having a functional group having a function as an anion receptor. The monomer may further include a monomer (C') different from the monomer (A') and the monomer (B').

[0138] Monomer (A') and monomer (B') may have an ethylenically unsaturated group. In this case, monomer (A') and monomer (B') may be polymerized by free radical addition polymerization. In this case, the monomers may be polymerized in the presence of an initiator. That is, the polymerization reaction may be carried out with a polymerizable composition comprising a monomer and an initiator.

[0139] The monomer (A') is a monomer from which the structural unit (A) is derived in the polymer. Examples of the monomer (A') include a monomer (A1') represented by the following formula (A1') and a monomer (A2') represented by the following formula (A2').

[0140] [Chemical formula 11]

[0141]

[0142] (X, Y and M of formula (A1') + Synonymous with formula (A1).

[0143] [Chemical formula 12]

[0144]

[0145] (In formula (A2'), R 15 ~R 17 R of formula (A2) 15 ~R 17 Synonymous, Y 2' is a compound that can be derived from Y in formula (A2) 2 The phenolic hydroxyl group corresponding to the -OM group possessed by the 2 The -SO3M group has a sulfonic acid group corresponding to the group. )

[0146] Y 2 ' can be used with Y 2 The same group may also be 2 That is, Y 2 'For the desired Y 2 A group having a group convertible into an -OM group or -SO3M group at the same position as the -OM group or -SO3M group.

[0147] As a derivative of Y 2 The group of the phenolic hydroxyl group corresponding to the -OM group possessed by the present invention may be, for example, a hydrolyzable group, which can be hydrolyzed to form a phenolic hydroxyl group with Y. 2 A phenolic hydroxyl group is introduced into the position corresponding to the -OM group. Examples of the hydrolyzable group include an alkoxide group or -OSi(R k )3 base (R k The phenolic hydroxyl group can be converted into an -OM group by reacting with a basic salt of an alkali metal such as MOH, M2CO3, or MHCO3.

[0148] Similarly, as a derivative of Y 2 The group of the sulfonic acid group corresponding to the -SO3M group possessed may include, for example, a sulfonic acid ester group, a -SO2Cl group, and the like, which are groups capable of deriving a sulfonic acid group (-SO3H). The sulfonic acid group may be converted into an -OM group by, for example, reacting with a salt of an alkali metal such as MOH, M2CO3, MHCO3, or an alkali metal halide. In addition, the -SO2Cl group may also be converted into an -SO3M group by reacting with MOH. In the case of using an excess of MOH, almost all of the -SO2Cl groups may also be converted into -SO3M groups. In this reaction, there is also a case where a portion of the -SO2Cl group forms an -SO3H group. Regarding the -SO3H group, it may be separately reacted with a base containing M to form an -SO3M group. In addition, Y 2 ' can be a 2 The same anion part and the group that forms a salt with a cation other than an alkali metal ion. In this case, the structural unit (A2) can be derived by subjecting the obtained polymer to a cation exchange reaction. The reaction rate of Y2' (Y 2 ' is converted into Y 2 The ratio) can be 85 mol% or more, 90 mol% or more, or 95 mol% or more.

[0149] Monomer (B’) is a monomer that derives the structural unit (B) in the polymer. As monomer (B’), monomers (B’) represented by the following formula (B’) can be cited.

[0150] [Chemical formula 13]

[0151]

[0152] (In the formula, R 1 ~R 3 and W are synonymous with R 1 ~R 3 and W in formula (B).)

[0153] The radical polymerization initiator can be either a thermal initiator or a photoinitiator. For example, as the thermal initiator, 2,2-azobis(isobutyronitrile) (AIBN) can be cited; azo-based initiators such as 2,2-azobis(2-methylbutyronitrile) (AMBN), 2,2-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1-azobis(1-cyclohexanecarbonitrile) (ACHN, V-40), dimethyl-2,2-azobisisobutyrate (MAIB), etc.; organic peroxides such as benzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, decanoyl peroxide, bis(2,4-dichlorobenzoyl) peroxide, etc. As the photoinitiator, oxime-based compounds, metallocene-based compounds, acylphosphine-based compounds, aminophenone compounds, etc. can be cited. One or more than two kinds of initiators can be used.

[0154] [Ionic conductive inorganic solid electrolyte]

[0155] As the ionic conductive inorganic solid electrolyte, there is no particular limitation, and it can be an oxide (oxide-based solid electrolyte), a sulfide (sulfide-based solid electrolyte), a hydride (hydride-based solid electrolyte), a halide (halide-based solid electrolyte), etc. The ionic conductive inorganic solid electrolyte can contain at least one of an alkali metal element and an alkaline earth metal element, and can also contain an alkali metal element.

[0156] (Oxide-based solid electrolyte)

[0157] As the oxide-based solid electrolyte, for example, perovskite-type oxides, NASICON-type oxides, LISICON-type oxides, garnet-type oxides, etc., and oxides doped with other cations or anions can be cited.

[0158] As the perovskite-type oxide, Li a La 1-a TiO3 (0 < a < 1) and other Li-La-Ti-based oxides, Lib La 1-b Li-La-Ta based oxides such as LaTaO3 (0 < b < 1), Li c La 1-c Li-La-Nb based oxides such as LaNbO3 (0 < c < 1), etc.

[0159] Examples of NASICON type oxides include Li 1+d Al d Ti 2-d (PO4)3 (0 ≤ d ≤ 1), etc. NASICON type oxides are oxides represented by Li m M 1 n M 2 o P p O q (wherein, M 1 is one or more elements selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Sb, and Se. M 2 is one or more elements selected from the group consisting of Ti, Zr, Ge, In, Ga, Sn, and Al. m, n, o, p, and q are arbitrary positive numbers.). Examples include Li 1+x+y Al x (Ti, Ge) 2-x Si y P 3-y O 12 (0 < x < 2, 0 < y < 3) (LATP), etc.

[0160] Examples of LISICON type oxides include oxides represented by Li4MO4 - Li3MO4 (M 3 is one or more elements selected from the group consisting of Si, Ge, and Ti. M 4 is one or more elements selected from the group consisting of P, As, and V.). etc. 3 is one or more elements selected from the group consisting of Si, Ge, and Ti. M 4 is one or more elements selected from the group consisting of P, As, and V.). etc.

[0161] Examples of garnet type oxides include Li7La3Zr2O 12 (LLZ), Li 7-a2 La3Zr 2-a2 Ta a2 O 12 (LLZT, where 0 < a2 < 1, or 0.1 < a2 < 0.8, or 0.2 < a2 < 0.6) and other Li-La-Zr based oxides, etc.

[0162] The oxide-based solid electrolyte can be a crystalline material or an amorphous material.

[0163] Examples of oxide-based solid electrolytes include Li 6.6 LqCy 1.6 Ta 0.4 O 12 , Li 0.33 La 0.55 TiO3, etc.

[0164] (Sulfide-based solid electrolyte)

[0165] As sulfide-based solid electrolytes, there are Li2S-P2S5 compounds, Li2S-SiS2 compounds, Li2S-GeS2 compounds, Li2S-B2S3 compounds, Li2S-P2S3 compounds, LiI-Si2S-P2S5, LiI-Li2S-P2O5, LiI-Li3PO4-P2S5, Li 10 GeP2S 12 wait.

[0166] It should be noted that in this specification, the expression "sulfide-based compound" referring to a sulfide-based solid electrolyte is used as a general term for solid electrolytes that mainly include raw materials such as "Li2S" and "P2S5" recorded before the "sulfide-based compound". For example, the Li2S-P2S5-based compound includes a solid electrolyte that includes Li2S and P2S5 and other raw materials. In addition, the Li2S-P2S5-based compound also includes a solid electrolyte in which the mixing ratio of Li2S and P2S5 is different.

[0167] Examples of Li2S-P2S5 compounds include Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-Z m S n (m and n are positive numbers. Z is Ge, Zn or Ga), etc.

[0168] As Li2S-SiS2 compounds, there are Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li2SO4, Li2S-SiS2-Li x MO y (x and y are positive numbers. M is P, Si, Ge, B, Al, Ga or In), etc.

[0169] As Li2S-GeS2 series compounds, Li2S-GeS2, Li2S-GeS2-P2S5 and the like can be listed.

[0170] The sulfide-based solid electrolyte may be a crystalline material or an amorphous material.

[0171] (Hydride-based solid electrolyte)

[0172] As hydride-based solid electrolyte materials, there can be listed LiBH4, LiBH4-3KI, LiBH4-PI2, LiBH4-P2S5, LiBH4-LiNH2, 3LiBH4-LiI, LiNH2, Li2AlH6, Li(NH2)2I, Li2NH, LiGd(BH4)3Cl, Li2(BH4)(NH2), Li3(NH2)I, Li4(BH4)(NH2)3, etc.

[0173] (Halide-based solid electrolyte)

[0174] Examples of the halide solid electrolyte include compounds containing Li, a metal element, and a halogen element.

[0175] The halide solid electrolyte may be a crystalline material or an amorphous material.

[0176] As ion-conductive inorganic solid electrolytes, compounds obtained by replacing part or all of the Li in the compounds listed as specific examples of oxide-based solid electrolytes, sulfide-based solid electrolytes, hydride-based solid electrolytes or halide-based solid electrolytes with Na, K, Rb or Cs can also be listed.

[0177] When the electrochemical resistance of the ion-conductive inorganic solid electrolyte is insufficient, the coating effect brought about by the coating material for battery components of this embodiment is particularly useful. As such an ion-conductive inorganic solid electrolyte, an electrolyte containing a reducing oxidizing metal element can be cited. As such an ion-conductive inorganic solid electrolyte, an electrolyte containing a reducing oxidizing metal element can be cited. + The electrolyte reacts at a potential range of -0.1 to 4.5 V.

[0178] As ion-conductive inorganic solid electrolytes, perovskite-type oxides, NASICON-type oxides, and LISICON-type oxides tend to have poor electrochemical resistance, and therefore can more effectively exert the effect of the battery member coating material.

[0179] The content of the ion-conductive inorganic solid electrolyte may be 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more relative to the total amount of the coating agent for battery components. In addition, the content of the ion-conductive inorganic solid electrolyte may be 95% by mass or less, 90% by mass or less, or 85% by mass or less relative to the total amount of the coating agent for battery components. In addition, the content of the ion-conductive inorganic solid electrolyte may be 50 to 95% by mass, 55 to 90% by mass, or 60 to 85% by mass relative to the total amount of the coating agent for battery components. The content of the ion-conductive inorganic solid electrolyte may be the amount of the ion-conductive inorganic solid electrolyte coated by the coating material for battery components formed by the coating agent for battery components.

[0180] The content of the ion-conductive inorganic solid electrolyte relative to the total amount of the coating agent for battery components may be 15% by volume or more, 25% by volume or more, 35% by volume or more, 40% by volume or more, 45% by volume or more, or 50% by volume or more. In addition, the content of the ion-conductive inorganic solid electrolyte relative to the total amount of the coating agent for battery components may be 90% by volume or less, 80% by volume or less, 70% by volume or less, or 60% by volume or less. In addition, the content of the ion-conductive inorganic solid electrolyte relative to the total amount of the coating agent for battery components may be 15 to 90% by volume, 25 to 80% by volume, or 35 to 60% by volume. The content of the ion-conductive inorganic solid electrolyte may be the content of the ion-conductive inorganic solid electrolyte in the layer formed by the coating agent for battery components.

[0181] The ion-conductive inorganic solid electrolyte may be a particle surface treated. Specifically, the surface non-conductive layer may be removed by using an acid, or a covalent bond may be formed with an atom. The acid is not particularly limited, and hydrochloric acid, nitric acid, phosphoric acid, etc. may be mentioned.

[0182] [Swelling agent]

[0183] The coating agent for battery components of the present embodiment may contain a swelling agent. Examples of the swelling agent include organic solvents and ionic liquids. The coating material for battery components formed from such a coating agent for battery components may contain a swelling agent.

[0184] (Ionic Liquids)

[0185] The ionic liquid is not particularly limited, and may be, for example, an ionic liquid that can be used for batteries and the like. Specifically, imidazolium salts, pyrrolidinium salts, piperidinium salts, pyridinium salts, quaternary ammonium salts, quaternary phosphonium salts, etc. may be cited. The coating agent for battery components of this embodiment may contain one or more ionic liquids. There are no particular restrictions on the anions possessed by the ionic liquid, and may be, for example, Cl - Br - ,I - 、ClO4 - PF6 - 、BF4 - CF3SO3 - 、(FSO2)2N - 、(CF3SO2)2N - , (C r F 2r+1 SO2)2N - (r is an integer greater than 2), HSO3 - From the perspective of electrochemical stability, PF6 - 、BF4 - CF3SO3 - 、(FSO2)2N - 、(CF3SO2)2N - or (C m F 2m+1 SO2)2N - , more preferably (CF3SO2)2N - The ionic liquid may be liquid at 25°C.

[0186] Examples of the pyrrolidinium cation contained in the pyrrolidinium salt include the following cations.

[0187] [Chemical formula 14]

[0188]

[0189] In the formula, R 41 and R 42 Each independently represents a monovalent organic group, and the organic group preferably has 1 to 15 carbon atoms. The monovalent organic group is an alkyl group having 1 to 15 carbon atoms such as a butyl group or a group represented by the formula: 1 -O-(A 2 -O) k -A 3 The group represented by (A 1 is an alkylene group having 1 or 2 carbon atoms, A 2 is an alkylene group having 2 or 3 carbon atoms, A 3 is an alkyl group having 1 to 3 carbon atoms, and k is 0 to 3. ).

[0190] As given by the formula:-A 1 -O-(A 2 -O) k -A 3 The group represented by is preferably a group having 1 to 10 carbon atoms, more preferably a -CH3OCH2CH2OCH3 group or -CH2CH2-O-CH3 group. 41 is an alkyl group having 1 to 3 carbon atoms, and may be a methyl group. 41 and R 42 They may be the same or different. It should be noted that the hydrogen bonded to the carbon atom constituting the pyrrolidine ring may be substituted with a substituent.

[0191] Examples of the piperidinium cation contained in the piperidinium salt include the following cations.

[0192] [Chemical formula 15]

[0193]

[0194] In the formula, R 43 and R 44 Each independently represents a monovalent organic group, and the organic group preferably has 1 to 15 carbon atoms. As the monovalent organic group, it is an alkyl group having 1 to 15 carbon atoms or a group represented by the formula: 1 -O-(A 2 -O) k -A 3 The group represented by (A 1 is an alkylene group having 1 or 2 carbon atoms, A 2 is an alkylene group having 2 or 3 carbon atoms, A 3 is an alkyl group having 1 to 3 carbon atoms, and k is 0 to 3. ).

[0195] R 44 The alkyl group of the formula: -A is more preferably an alkyl group having 2 to 6 carbon atoms such as a butyl group. 1 -O-(A 2 -O) k -A 3 The group represented by is preferably a group having 1 to 10 carbon atoms, more preferably a -CH3OCH2CH2OCH3 group or -CH2CH2-O-CH3 group. 43 is an alkyl group having 1 to 3 carbon atoms, and may be a methyl group. 43 and R 44 They may be the same or different. It should be noted that the hydrogen bonded to the carbon atom constituting the piperidine ring may be substituted with a substituent.

[0196] Examples of the imidazolium cation contained in the imidazolium salt include the following cations.

[0197] [Chemical formula 16]

[0198]

[0199] In the formula, R 46 and R 47 Each independently represents a monovalent organic group, and the organic group preferably has 1 to 15 carbon atoms. As the monovalent organic group, it is an alkyl group having 1 to 15 carbon atoms or a group represented by the formula: 1 -O-(A 2 -O) k -A 3 The group represented by (A 1 is an alkylene group having 1 or 2 carbon atoms, A 2 is an alkylene group having 2 or 3 carbon atoms, A 3 is an alkyl group having 1 to 3 carbon atoms, and k is 0 to 3. ).

[0200] As R 47 The alkyl group is preferably an alkyl group having 2 to 6 carbon atoms such as a butyl group. 1 -O-(A 2 -O) k -A 3 The group represented by is preferably a group having 1 to 10 carbon atoms, more preferably a -CH3OCH2CH2OCH3 group or -CH2CH2-O-CH3 group. 46 is an alkyl group having 1 to 3 carbon atoms, and may be a methyl group. 46 and R 47 They may be the same or different. It should be noted that the hydrogen bonded to the carbon atom constituting the imidazole ring may be substituted with a substituent.

[0201] As the ammonium cation of the quaternary ammonium salt, for example, the following cations can be mentioned.

[0202] [Chemical formula 17]

[0203]

[0204] In the formula, R 51 ~R 54 Each independently represents a monovalent organic group, and the organic group preferably has 1 to 15 carbon atoms. As the monovalent organic group, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula: 1 -O-(A 2 -O) k -A 3 The group represented by (A 1 is an alkylene group having 1 or 2 carbon atoms, A 2is an alkylene group having 2 or 3 carbon atoms, A 3 is an alkyl group having 1 to 3 carbon atoms, and k is 0 to 3. ) R 51 ~R 54 All of them may be the same, or two or more different groups may be used. 51 is an alkyl group having 1 to 10 carbon atoms, R 52 ~R 54 is an alkyl group having 1 to 3 carbon atoms, more preferably R 51 is an alkyl group having 3 to 8 carbon atoms such as butyl, 52 ~R 54 Methyl or ethyl. 1 -O-(A 2 -O) k -A 3 The group represented by is preferably a group having 1 to 10 carbon atoms, more preferably a -CH3OCH2CH2OCH3 group or -CH2CH2-O-CH3.

[0205] Examples of the phosphonium cations contained in the quaternary phosphonium salt include the following cations.

[0206] [Chemical formula 18]

[0207]

[0208] In the formula, R 56 ~R 59 Each independently represents a monovalent organic group, and the organic group preferably has 1 to 15 carbon atoms. As the monovalent organic group, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula: 1 -O-(A 2 -O) k -A 3 The group represented by (A 1 is an alkylene group having 1 or 2 carbon atoms, A 2 is an alkylene group having 2 or 3 carbon atoms, A 3 is an alkyl group having 1 to 3 carbon atoms, and k is 0 to 3. ) R 56 ~R 59 All of them may be the same, or two or more different groups may be used. 56 is an alkyl group having 1 to 10 carbon atoms, R 57 ~R 59 is an alkyl group having 1 to 3 carbon atoms, more preferably R 56 is an alkyl group having 3 to 8 carbon atoms such as pentyl, 57 ~R 59 It is methyl or ethyl.

[0209] Specific examples of the ionic liquid include 1-(2-methoxyethoxymethyl)-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-n-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, 1-n-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-n-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, triethyl-n-pentylphosphonium bis(trifluoromethanesulfonyl)imide, and n-butyltrimethylammonium bis(trifluoromethanesulfonyl)imide.

[0210] The content of the ionic liquid may be 5 to 45% by volume, 10 to 40% by volume, or 20 to 35% by volume relative to the total amount of the coating agent for a battery member.

[0211] [Organic solvents]

[0212] The organic solvent may be an aprotic solvent, and for example, may be at least one selected from the group consisting of carbonate-based solvents, fluorine-based solvents, and ether-based solvents.

[0213] As carbonate solvents, chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate can be listed. As ether solvents, cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, and 1,3-dioxolane can be listed; chain ethers such as 1,2-diethoxyethane and ethoxymethoxyethane can be listed. As fluorine solvents, hydrofluorocarbons such as perfluorooctane can be listed; hydrofluoroethers such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether, and hydrofluoroolefins such as 1,3,3,3-tetrafluoropropylene can be listed. In addition, as solvents, aprotic solvents such as dimethyl sulfoxide (DMSO); amide solvents such as dimethylformamide (DMF) and dimethylacetamide (DMA) can be listed. The organic solvent can be used alone or as a mixed solvent containing two or more organic solvents.

[0214] When a mixed solvent is used, for example, the organic solvent may be a mixed solvent containing two or more carbonate-based solvents, a mixed solvent containing two or more cyclic carbonates, or a mixed solvent containing ethylene carbonate and propylene carbonate.

[0215] The content of the swelling agent may be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more relative to the total amount of the coating agent for the battery component. In addition, the content of the swelling agent may be 90% by mass or less, 85% by mass or less, or 80% by mass or less relative to the total amount of the coating agent for the battery component.

[0216] The content of the swelling agent may be 5% by volume or more, 10% by volume or more, 20% by volume or more, 30% by volume or more, 40% by volume or more, or 50% by volume or more relative to the total amount of the coating agent for the battery component. In addition, the content of the swelling agent may be 90% by volume or less, 80% by volume or less, 70% by volume or less, or 60% by volume or less relative to the total amount of the coating agent for the battery component.

[0217] The mass ratio of the polymer to the swelling agent in the coating agent for battery components or the coating material for battery components may be 1:0.1 to 1:4, 1:0.3 to 1:3.5, 1:0.5 to 1:3, or 1:1 to 1:2.5. In the coating material for battery components or the coating agent for battery components, the polymer may swell due to the swelling agent. The coating material for battery components may be in a gel state.

[0218] When the content of the ion conductive inorganic solid electrolyte in the battery member coating agent is less than 5 mass %, the content of the swelling agent may be 30 to 90 mass %, or 50 to 84 mass % based on the total amount of the battery member coating agent.

[0219] When the content of the ion conductive inorganic solid electrolyte in the battery member coating agent is 5 mass % or more, the content of the swelling agent may be 3 to 70 mass %, 5 to 50 mass %, or 7 to 30 mass % relative to the total amount of the battery member coating material.

[0220] The coating agent for battery components of this embodiment is preferably in the range of Li / Li + The reference is stabilization in the potential range of -0.1 to 4.5 V. Stabilization means that the reaction rate of the electrochemical reaction occurring in either the electrolyte or the electrode is reduced or the reaction no longer occurs compared to the case where the battery member coating material is not present.

[0221] The coating material for battery components of the present embodiment can be used as a constituent material of electrochemical devices such as capacitors and batteries, for example, it can be used as a material for the electrolyte of a battery. In particular, when the coating material for battery components includes an ion-conductive inorganic solid electrolyte, it can also be used as an electrolyte composition for forming an electrolyte. The electrolyte can be formed by press-molding the electrolyte composition. That is, the electrolyte of the present embodiment includes the coating material for battery components of the present embodiment. As batteries, lithium ion batteries, sodium ion batteries, and other batteries that are charged and discharged by the migration of alkali metal ions can be listed. The battery can be a primary battery, a secondary battery, or an all-solid-state battery. The electrolyte composition of the present embodiment can be a non-liquid electrolyte composition such as a solid electrolyte composition.

[0222] The battery of the present embodiment includes a positive electrode, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode. The electrolyte may include the coating material of the present embodiment. Examples of the coating material include: (1) a coating material that covers individual particles of an ion-conductive inorganic solid electrolyte contained in the electrolyte; (2) a coating material (which may be a coating layer) is formed on the surface of at least one of the negative electrode and the positive electrode and an electrolyte is formed on the coating material; (3) a coating material (which may be a coating layer) for a battery component that includes an electrolyte and covers at least a portion of the surface of the electrolyte (electrolyte with a coating). In the case of (2), the coating material may be formed on the surface of the negative electrode. In the case of (2), the electrolyte may be in the form of a sheet. In the case of (3), the coating material may be formed on both sides of the electrolyte. In the case of (3), an electrode may be formed on the coating material. In (3), when the electrolyte is in the form of a sheet, a layer of the coating material may be formed on a portion or the entire surface of at least one main surface, and a layer of the coating material may be formed on a portion or the entire surface of both main surfaces. When a layer of the coating material is formed only on one main surface, the negative electrode can be formed on the coating material.

[0223] For example, in the case of a lithium ion battery, the positive electrode is not particularly limited, and may be a positive electrode containing a positive electrode active material and, if necessary, a conductive auxiliary agent, a binder, and the like.

[0224] The positive electrode may be formed by forming a layer containing these materials on the current collector. Examples of positive electrode active materials include lithium (Li) and at least one transition metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and Al. Examples of such lithium composite metal oxides include LiCoO2, LiNiO2, LiMn2O4, Li2MnO3, LiNi x Mn y Co 1-x-yO2[0 <x+y<1])、LiNi x Co y Al 1-x-y O2[0 <x+y<1])、LiCr 0.5 Mn 0.5 O2, LiFePO4, Li2FeP2O7, LiMnPO4, LiFeBO3, Li3V2(PO4)3, Li2CuO2, Li2FeSiO4, Li2MnSiO4, etc.

[0225] The lithium ion battery may have a separator. The separator may be a porous material or a porous material made of resin. Specifically, porous polyolefin membranes, porous ceramic membranes, etc. may be mentioned.

[0226] The negative electrode of the lithium ion battery is not particularly limited, and may be a negative electrode containing a negative electrode active material and, if necessary, a conductive auxiliary agent, a binder, etc. For example, single substances of elements such as Li, Si, P, Sn, Si-Mn, Si-Co, Si-Ni, In, Au, and alloys or composites containing these elements, carbon materials such as graphite, and materials with lithium ions inserted between the layers of the carbon materials, etc. may be cited.

[0227] As a method for manufacturing a coating agent for battery components, there is no particular limitation as long as it is a method that can mix the various components of the coating agent for battery components, and a method (solid phase method) of mixing the various components of the coating agent for battery components with a mortar or the like can be cited. In addition, in the case where the coating agent for battery components contains an ionic liquid, a method (liquid phase method) of dissolving and dispersing the various components of the coating agent for battery components in an organic solvent to manufacture a precursor composition and removing the organic solvent from the precursor composition by drying or the like can also be cited. As an organic solvent used in the liquid phase method, it can be an aprotic solvent, and N-methyl-2-pyrrolidone and the like can be cited. The amount of the organic solvent used can be 200 to 2000 parts by mass, or 500 to 1500 parts by mass relative to 100 parts by mass of the coating agent for battery components manufactured. For an ion-conductive inorganic solid electrolyte, an acid treatment can be performed before mixing with other components.

[0228] As a manufacturing method of the battery of the present embodiment, for example, there may be a process of preparing an electrolyte composition (battery component coating agent) and a process of pressurizing the electrolyte composition to manufacture an electrolyte. The manufactured electrolyte is arranged between the positive electrode and the negative electrode. Pressurization can be carried out by arranging the electrolyte composition on the negative electrode or the positive electrode or between the positive electrode and the negative electrode. The pressure during pressurization can be, for example, 10 to 300 MPa, or 100 to 250 MPa. Pressurization can be carried out at, for example, 10°C to 60°C or 20°C to 50°C. In the case where the battery component coating agent contains an organic solvent, in order to prevent the evaporation of the organic solvent, it can be carried out below the boiling point of the organic solvent (below the lowest boiling point of the organic solvents contained in the case of containing multiple organic solvents).

[0229] Example

[0230] [Manufacturing of polymers having the ability to preferentially conduct metal ions]

[0231] A copolymer of the monomer A1 represented by the following formula and styrene (in a molar ratio of 54:46) was produced as follows.

[0232] [Chemical formula 19]

[0233]

[0234] First, monomer A1 was produced as follows.

[0235] (Synthesis of Monomer A1)

[0236] Under nitrogen atmosphere, trifluoromethanesulfonamide (52.5 mmol, 7.83 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in dehydrated acetonitrile (150 mL, manufactured by Kanto Chemical Co., Ltd.). To the solution, lithium hydroxide (105 mmol, 2.51 g, manufactured by Tokyo Chemical Industry Co., Ltd.) and 4-acetamidobenzenesulfonyl chloride (50 mmol, 11.68 g, manufactured by Tokyo Chemical Industry Co., Ltd.) were added in sequence and heated under reflux for 5 hours. After cooling to room temperature, an excess of acetonitrile (700 mL) was added to precipitate a solid, which was separated by filtration and washed with dichloromethane (manufactured by Kanto Chemical Co., Ltd.) to obtain Intermediate 1. The yield was 97.1%.

[0237] The structural formula of intermediate 1:

[0238] [Chemical formula 20]

[0239]

[0240] Under nitrogen atmosphere, 5% hydrochloric acid (22.5 mL) was added to intermediate 1 (15 mmol, 5.28 g), and stirred at 90°C for 2 hours. After cooling to room temperature, lithium hydroxide aqueous solution was added until the pH reached 7 or above based on the confirmation of pH test paper, and then a solid was obtained by drying under reduced pressure. The obtained solid was extracted with acetonitrile solution and dried under reduced pressure to obtain intermediate 2. The yield was 92.6% based on the raw material of the above intermediate 1.

[0241] The structural formula of intermediate 2:

[0242] [Chemical formula 21]

[0243]

[0244] Maleic anhydride (13.3 mmol, 1.30 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in dehydrated 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.) under a nitrogen atmosphere. A solution of all intermediate 2 (13.2 mmol, 4.09 g) prepared under a nitrogen atmosphere in dehydrated tetrahydrofuran (26.4 mL, manufactured by Kanto Chemical Co., Ltd.) was added dropwise to the solution, and stirred at room temperature for 12 hours. After the reaction, the precipitate was filtered and vacuum dried at 60°C for 4 hours to obtain a solid containing intermediate 3.

[0245] The structural formula of intermediate 3:

[0246] [Chemical formula 22]

[0247]

[0248] Under nitrogen atmosphere, a solid containing intermediate 3 (14.0 mmol, 5.70 g) and an aqueous sodium acetate solution (13.3 mmol, 1.09 g, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to anhydrous acetic acid (12.3 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 70°C for 3 hours. The entire solution after the reaction was added dropwise to an excess of diethyl ether (manufactured by Kanto Chemical Co., Ltd.) at 0°C, and the precipitate was recovered by filtration. Under an inert atmosphere, the precipitate was extracted with dehydrated acetonitrile (manufactured by Kanto Chemical Co., Ltd.) and dried under reduced pressure to obtain monomer A1. The overall yield of all steps was 72.8%.

[0249] The monomer A1: 3.121 g, styrene: 0.833 g, and AIBN: 57.5 mg were dissolved in 70 mL of dehydrated acetonitrile, and tetralin was added as an internal standard substance. The reaction was carried out at 60°C under a nitrogen atmosphere for 24 hours while confirming the monomer consumption rate. The polymerization solution was dialyzed in acetonitrile and vacuum dried at 120°C to obtain 3.50 g (yield 89%) of polymer. The monomer introduction ratio was A1: styrene = 54:46. The monomer introduction ratio was adjusted by the copolymer 1 H-NMR was calculated. Styrene was used by sealing a commercial reagent with a purity of >98% manufactured by Sigma-Aldrich Co. LLC with CaCl2 and drying overnight, and then adding CaH2 and performing vacuum distillation to increase the purity.

[0250] The number average molecular weight of the synthesized polymer is Mn = 9.3×10 4 , weight average molecular weight Mw = 3.0 × 10 5 , molecular weight distribution Mw / Mn=3.19.

[0251] [Ion-conductive inorganic solid electrolyte]

[0252] As the ion-conductive inorganic solid electrolyte, granular (average particle size: 1 μm) LATP powder: LICGC PW-01 Powder manufactured by Ohara Corporation was used.

[0253] [Manufacturing of Electrolyte Composition]

[0254] (Example 1)

[0255] The polymer having the ability to preferentially conduct metal ions produced as described above was mixed with an organic solvent (ethylene carbonate:propylene carbonate=1:1 (volume ratio)) (KISHIDA CHEMICAL Co., Ltd.) to produce a gel polymer composition. Next, the gel polymer composition and LATP powder were mixed using a mortar so that the content of the LATP powder in the electrolyte composition was 70% by mass to obtain an electrolyte composition.

[0256] (Example 1')

[0257] The polymer having the ability to preferentially conduct metal ions produced as described above was mixed in an amount of 16 mass %, LATP powder in an amount of 79 mass %, and polytetrafluoroethylene (PTFE) in an amount of 5 mass %, and 150 mg of the mixture was press-molded at a pressure of 200 MPa to obtain a pellet molded body having a diameter of 1.5 cm. 32 mass % of an organic solvent (ethylene carbonate:propylene carbonate=1:1 (volume ratio)) (KISHIDA CHEMICAL Co., Ltd.) was infiltrated into the pellet molded body relative to 100 mass % of the pellet molded body to obtain an electrolyte composition.

[0258] (Example 2)

[0259] On both sides of a sheet-like LATP sintered body (length 1 cm×width 1 cm×thickness 90 μm), a coating material 1 for battery components was prepared by adding 200 parts by mass of an organic solvent (ethylene carbonate:propylene carbonate=1:1 (volume ratio)) (KISHIDA CHEMICAL Co., Ltd.) to 100 parts by mass of a polymer having the ability to preferentially conduct metal ions produced as described above, thereby obtaining an electrolyte composition. (Coating material 1 for battery components / LATP sintered body / Coating material 1 for battery components)

[0260] (Example 3)

[0261] A coating material 2 for battery components was prepared by adding 50 parts by mass of poly(vinylidene fluoride-co-hexafluoropropylene) and 300 parts by mass of an organic solvent (ethylene carbonate:propylene carbonate=1:1 (volume ratio)) (KISHIDA CHEMICAL Co., Ltd.) to 100 parts by mass of the polymer having the ability to preferentially conduct metal ions produced as described above, and an electrolyte composition was obtained. (Coating material 2 for battery components / LATP sintered body / Coating material 2 for battery components)

[0262] (Comparative Example 1)

[0263] LATP sintered body: LICGC sintered body-01 manufactured by Ohara Co., Ltd. was used as it is.

[0264] (Cyclic test)

[0265] An evaluation cell of a coin-shaped battery CR2032 was assembled in a glove box under a dry argon atmosphere. Specifically, each layer was stacked in the evaluation cell in the following order to produce a test stack.

[0266] (lithium / electrolyte composition / lithium)

[0267] The evaluation cell was subjected to a current of +100 μA / cm 2 and -100μA / cm 2 The test was conducted alternately for 1 hour, and the time until a short circuit occurred was defined as the cycle life.

[0268] Figure 1 : is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Example 1. Figure 1 As shown, at 100μA / cm 2 Under the condition of constant current density, it is stable for more than 100 cycles. Figure 2 : is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Comparative Example 1. In the case of Comparative Example 1, the cycle life was only 6 cycles. Based on these experimental results, it is considered that a short circuit occurred in Comparative Example 1 due to the reduction of LATP by lithium, and it can be seen that the coating material of this embodiment in Example 1 contributes to improving the reduction resistance of LATP.

[0269] Figure 3 This is a graph showing the results of a cycle test on a single cell using the electrolyte composition of Example 2. Figure 4 : is a graph showing the results of the cycle test on the single cell using the electrolyte composition of Example 3. For the single cells using the electrolyte compositions of Examples 2 and 3, also at 100 μA / cm 2 Under the condition of constant current density, it is stable for more than 100 cycles.

[0270] The results of the cycle test of the single cell using the electrolyte composition of Example 1' were stable over 50 cycles.

Claims

1. A coating material for a battery member, comprising a polymer having the ability to preferentially conduct metal ions. 2 . The battery member coating material according to claim 1 , which is used for coating an ion-conductive inorganic solid electrolyte.

3. The coating material for a battery member according to claim 2, wherein The ion conductive inorganic solid electrolyte is in the form of Li / Li + The reaction occurs in the potential range of -0.1 to 4.5 V. 4 . The battery member coating material according to claim 1 , further comprising a swelling agent.

5. The coating material for a battery member according to claim 4, wherein The swelling agent is at least one of an organic solvent and an ionic liquid.

6. The coating material for a battery member according to claim 1 or 2, wherein The polymer has at least one of an anionic functional group having a metal ion as a counter cation and a functional group having an anion capturing ability.

7. The coating material for battery components according to claim 1 or 2, wherein the coating material has a Li / Li + The potential range of -0.1 to 4.5 V is stabilized.

8. The coating material for a battery member according to claim 2, wherein The ion-conductive inorganic solid electrolyte is in the form of particles.

9. The coating material for a battery member according to claim 2, wherein The ion-conductive inorganic solid electrolyte is in sheet form. 10 . An electrolyte comprising the coating material for a battery member according to claim 1 or 2 .

11. A coated electrolyte comprising an electrolyte and a battery component coating material covering at least a portion of a surface of the electrolyte, wherein the battery component coating material contains a polymer having an ability to preferentially conduct metal ions. 12 . A battery comprising the coating material for a battery member according to claim 1 .

13. A coating agent for a battery member, comprising a polymer having an ability to preferentially conduct metal ions.

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