Electrode material, positive electrode material, negative electrode material, positive electrode, negative electrode and battery

Abstract

An electrode material containing an electrode active material and a polymer having the ability to preferentially conduct metal ions, the ratio of the volume of the polymer to the total volume of the electrode active material and the polymer being 0.01-0.65.

Description

Technical Field

[0001] The present invention relates to electrode materials, positive electrode materials, negative electrode materials, positive electrodes, negative electrodes, and batteries. Background Art

[0002] Batteries such as lithium ion batteries that perform charge and discharge with the migration of metal ions between the positive electrode and the negative electrode are being actively studied because of their high capacity. As electrolytes for lithium ion batteries and the like, solutions containing lithium salts including organic solvents or ionic liquids are known, but research on solid electrolytes is underway from the viewpoints of safety and processability (Patent Documents 1 to 3). As solid electrolytes, various compounds such as oxide-based solid electrolytes and sulfide-based solid electrolytes are known.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Chinese Patent Application Specification No. 110247111

[0006] Patent Document 2: Korean Patent No. 10-2094466 Gazette

[0007] Patent Document 3: Chinese Patent Application Specification No. 112397762 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] Here, the adhesion between the material forming the negative electrode or the positive electrode and other components is insufficient, and improvement of the peel strength is desired. On the other hand, in order to improve the peel strength, a method of blending a polymer or the like has also been proposed. However, as a result of research by the present inventors, it has been found that in this case, since the transference number of alkali metal ions is low, the alkali metal ions do not flow uniformly, and there is a problem of a decrease in the capacity retention rate.

[0010] The present disclosure has been made in view of the above problems, and an object thereof is to provide an electrode material excellent in peel strength and capacity retention rate, and a positive electrode, a negative electrode, and a battery including the electrode material.

[0011] Means for Solving the Problems

[0012] The present disclosure includes the following embodiments [1] to

[15] .

[0013] [1] An electrode material containing an electrode active material and a polymer having the ability to preferentially conduct metal ions,

[0014] The ratio of the volume of the polymer to the total volume of the electrode active material and the polymer is 0.01 to 0.65.

[0015] [2] A positive electrode material containing a positive electrode active material and a polymer having the ability to preferentially conduct metal ions,

[0016] The ratio of the volume of the above polymer to the total volume of the above positive electrode active material and the above polymer is 0.03 to 0.50.

[0017] [3] A positive electrode material containing a positive electrode active material and a polymer having the ability to preferentially conduct metal ions,

[0018] The ratio of the mass of the above polymer to the total mass of the above positive electrode active material and the above polymer is 0.01 to 0.30.

[0019] [4] The positive electrode material according to [2] or [3], wherein the above polymer has at least one of an anionic functional group having an alkali metal ion as a counter cation and a functional group having an anion capturing ability.

[0020] [5] The positive electrode material according to any one of [2] to [4], further comprising a binder resin.

[0021] [6] The positive electrode material according to any one of [2] to [5], wherein the positive electrode material contains a nickel-containing alkali metal composite oxide.

[0022] [7] A positive electrode comprising the positive electrode material according to any one of [2] to [6].

[0023] [8] A battery comprising the positive electrode according to [7].

[0024] [9] A negative electrode material containing a negative electrode active material and a polymer having the ability to preferentially conduct metal ions,

[0025] The ratio of the volume of the above polymer to the total volume of the above negative electrode active material and the above polymer is 0.03 to 0.65.

[0026]

[10] A negative electrode material containing a negative electrode active material and a polymer having the ability to preferentially conduct metal ions,

[0027] The ratio of the mass of the above polymer to the total mass of the above negative electrode active material and the above polymer is 0.01 to 0.32.

[0028]

[11] The negative electrode material according to [9] or

[10] , wherein the above polymer has at least one of an anionic functional group having an alkali metal ion as a counter cation and a functional group having an anion capturing ability.

[0029]

[12] The negative electrode material according to any one of [9] to

[11] further includes a binder resin.

[0030]

[13] The negative electrode material according to any one of [9] to

[12] , wherein the negative electrode active material includes at least one selected from an oxide containing titanium, an active material containing silicon, and a carbon material.

[0031]

[14] A negative electrode including the negative electrode material according to any one of [9] to

[13] .

[0032]

[15] A battery including the negative electrode described in

[14] .

[0033] Advantages of the Invention

[0034] According to the present disclosure, it is possible to provide an electrode material excellent in peel strength and capacity retention rate, and a positive electrode, a negative electrode, and a battery including the electrode material. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a graph showing the results of charge and discharge tests of a battery using the positive electrode material of Example 1 and electrolyte composition 1.

[0036] Figure 2 It is a graph showing the results of charge and discharge tests of a battery using the positive electrode material of Comparative Example 1 and electrolyte composition 1.

[0037] Figure 3 It is a differential capacity curve of the results of charge and discharge tests of a battery using the positive electrode material of Example 1 and electrolyte composition 1.

[0038] Figure 4 It is a differential capacity curve of the results of charge and discharge tests of a battery using the positive electrode material of Comparative Example 1 and electrolyte composition 1.

[0039] Figure 5 It is a graph showing the results of charge and discharge tests of a half-cell using the negative electrode material of Example 2.

[0040] Figure 6 It is a graph showing the results of charge and discharge tests of a full cell using the electrode materials of Examples 1 and 2.

[0041] Figure 7 It is a graph showing the results of charge and discharge tests of a battery using the positive electrode material of Example 1' and electrolyte composition 2.

[0042] Figure 8 It is a graph showing the results of charge and discharge tests of a battery using the positive electrode material of Example 1'' and electrolyte composition 2. DETAILED DESCRIPTION OF THE INVENTION

[0043] The electrode material of this embodiment contains an electrode active material and a polymer having the ability to preferentially conduct metal ions, and the volume ratio of the polymer to the total volume of the electrode active material and the polymer is 0.01 to 0.65. Such an electrode material has excellent peel strength and a high transference number of alkali metal ions, and thus has an excellent capacity retention rate.

[0044] The electrode active material can be either a positive electrode active material or a negative electrode active material. When the electrode material is a positive electrode material (i.e., when the electrode active material is a positive electrode active material), for example, materials that satisfy at least one of the following (1) and (2) can be cited.

[0045] (1) The volume ratio of the polymer to the total volume of the positive electrode active material and the polymer is 0.03 to 0.50.

[0046] (2) The mass ratio of the above polymer to the total mass of the positive electrode active material and the polymer is 0.01 to 0.30.

[0047] Regarding (1), the volume ratio of the polymer in the positive electrode material to the total volume of the positive electrode active material and the polymer can be 0.03 to 0.40. Regarding (2), the mass ratio of the above polymer to the total mass of the positive electrode active material and the polymer can be 0.01 to 0.15.

[0048] As the positive electrode active material, for example, alkali metal composite oxides containing an alkali metal element and at least one metal element selected from transition metal elements and Al can be cited. The transition metal element can be at least one selected from V, Cr, Mn, Fe, Co, Ni, and Cu, and nickel can be included. For example, when the alkali metal element is lithium (i.e., in the case of a lithium composite oxide), as the lithium composite oxide, for example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNi x Mn y Co 1-x-y O 2 [0 < x + y < 1]), LiNi x Co y Al 1-x-y O 2 [0 < x + y < 1]), LiCr 0.5 Mn 0.5 O 2 , LiFePO 4 , Li 2FeP 2 O 7 、LiMnPO 4 、LiFeBO 3 、Li 3 V 2 (PO 4 ) 3 、Li 2 CuO 2 、Li 2 FeSiO 4 、Li 2 MnSiO 4 etc. When the positive electrode active material in the positive electrode material contains an alkali metal element other than Li, as a specific example, an example in which Li in the above specific example is replaced by another alkali metal can be cited. As the alkali metal other than Li, Na or K can be cited.

[0049] The content of the positive electrode active material in the positive electrode material may be 50% by mass or more, may be 60% by mass or more, and may be 70% by mass or more with respect to the total amount of the positive electrode material. The content of the positive electrode active material in the positive electrode material may be 99% by mass or less, may be 95% by mass or less, and may be 90% by mass or less with respect to the total amount of the positive electrode material. In addition, the content of the positive electrode active material in the positive electrode material may be 50 to 99% by mass, may be 60 to 95% by mass, and may be 70 to 90% by mass with respect to the total amount of the positive electrode material.

[0050] When the electrode material is a negative electrode material (that is, when the electrode active material is a negative electrode active material), for example, a material that satisfies at least one of the following (3) and (4) can be cited.

[0051] (3) The ratio of the volume of the polymer to the total volume of the negative electrode active material and the polymer is 0.03 to 0.65.

[0052] (4) The ratio of the mass of the above polymer to the total mass of the negative electrode active material and the polymer is 0.01 to 0.32.

[0053] As the negative electrode active material, elemental substances of alkali metal elements, Si, P, Sn, Si-Mn, Si-Co, Si-Ni, In, Au, etc., alloys or composites containing these elements, carbon materials such as graphite, substances in which alkali metal ions are intercalated between the layers of the carbon material, and titanium-containing oxides, etc. can be cited. Specifically, the negative electrode active material can contain at least one selected from titanium-containing oxides, silicon-containing active materials, and carbon materials. As the silicon-containing active material, silicon, silicon oxide (SiOx, 1≤x≤2), silicon-containing alloys, etc. can be cited. As the carbon material, graphite, hard carbon black, etc. can be cited. The alkali metal element can be Li, Na or K, can be Li or Na, and can be Li.

[0054] As the titanium-containing oxide, it can be a compound represented by the compositional formula: A s TiO t (where A is an alkali metal element, s≥0). Here, the alkali metal element A can be Li, Na or K, can be Li or Na, and can be Li. In the above compositional formula, s can be 0.1 to 2, can be 0.3 to 1.5, and can be 0.5 to 1. In the above compositional formula, t can be 2 to 3, or can be 2.2 to 2.8. Specifically, as the titanium-containing oxide, A 4 Ti 5 O 12 (A is an alkali metal, which can be Li).

[0055] The content of the negative electrode active material in the negative electrode material can be 50% by mass or more, can be 60% by mass or more, and can be 70% by mass or more with respect to the total amount of the negative electrode material. The content of the negative electrode active material in the negative electrode material can be 99% by mass or less, can be 95% by mass or less, and can be 90% by mass or less with respect to the total amount of the negative electrode material. In addition, the content of the negative electrode active material in the negative electrode material can be 50 to 99% by mass, can be 60 to 95% by mass, and can be 70 to 90% by mass.

[0056] [Polymer having the ability to preferentially conduct metal ions]

[0057] As the polymer having the ability to preferentially conduct metal ions (hereinafter also simply referred to as polymer), for example, when measuring the transference number of metal ions for at least one of the following (A) and (B) at room temperature (25°C), it can be a polymer in which the transference number of metal ions is 0.45 or more, 0.5 or more, 0.6 or more, or 0.7 or more.

[0058] (A) A composition containing 17% by mass of the polymer, 17% by mass of polyvinylidene fluoride (PVDF), and 66% by mass of a non-ionic plasticizer.

[0059] (B) A composition containing 31.9% by mass of the polymer and the remaining total amount of metal salts and non-ionic plasticizers, with a metal ion concentration of 0.3 mol / L.

[0060] When the polymer has an anionic functional group, the metal ions contained in the composition can be the counter cations of the anionic functional group or substances added in the form of metal salts. The polymer having the ability to preferentially conduct metal ions can be a polymer having the ability to preferentially conduct alkali metal ions. As the non-ionic plasticizer, organic solvents can be listed in composition (A), and at least one of organic solvents and other resins such as fluororesins can be listed in composition (B). The organic solvent can be an aprotic solvent. The aprotic solvent can be at least one selected from carbonate solvents, fluorine solvents, and ether solvents. As the fluororesin, resins having a carbon chain as the main chain such as polyvinylidene fluoride (PVDF) are preferred. The carbon chain can be formed by radical polymerization of ethylenically unsaturated groups.

[0061] As the carbonate solvents, chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate can be listed; cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate can be listed, etc. As the 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, etc. As the fluorine solvents, hydrofluorocarbons such as perfluorooctane can be listed; hydrofluoroethers such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether, hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene can be listed, etc. In addition, as the 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. The organic solvent can be a mixed solvent of ethylene carbonate:propylene carbonate = 1:1 (volume ratio).

[0062] The concentration of metal ions in the composition can be adjusted by adding metal salts. For example, when the metal salt is an alkali metal salt, there is no particular limitation on the alkali metal salt. Let the alkali metal be M, and MF, MCl, MBr, MI, MClO 4 、MPF 6 、MBF 4 、M 2 SO 4 、M[(C h F 2h+1 )SO 3 (h is 0 to 3), M[(C h F 2h+1)SO 2 ) 2 N (where h is from 0 to 3), etc. When the polymer has the following structural unit (A), M can be the same alkali metal element as the alkali metal element possessed by the structural unit (A).

[0063] As the polymer having the ability to preferentially conduct metal ions, a polymer containing at least one of an anionic functional group (also referred to as functional group (A).) having an alkali metal ion as a counter cation and a functional group having an anion-trapping ability (also referred to as functional group (B).) can be cited. As the structure of the polymer, there is no particular limitation, and a polymer having a carbon chain as the main chain can be cited, and this carbon chain can be formed by radical addition polymerization of a monomer having an ethylenically unsaturated group.

[0064] As the alkali metal ions that are counter cations of functional group (A), lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, etc. can be cited, and can be lithium ions, sodium ions or potassium ions, can be lithium ions or sodium ions, and can be lithium ions. Hereinafter, the structural unit containing functional group (A) and the metal ion that is the counter cation of functional group (A) will also be referred to as structural unit (A). Structural unit (A) can have a structure obtained by radical addition polymerization of a monomer having an ethylenically unsaturated group. The alkali metal ions that are counter cations of functional group (A) can contain the same alkali metal ions as the alkali metal ions contained in the positive electrode active material.

[0065] Structural unit (A) can have at least one selected from the conjugate anions of sulfonylimide group, the conjugate anions of sulfonic acid group, the conjugate anions of carboxylic acid group, and the conjugate anions of phenolic hydroxyl group as functional group (A). The conjugate anions of sulfonylimide group, the conjugate anions of sulfonic acid group, and the conjugate anions of phenolic hydroxyl group can be contained, for example, in the groups having conjugate anions of sulfonylimide group, the groups having conjugate anions of sulfonic acid group (sulfonic acid ester group), and the groups having conjugate anions of phenolic hydroxyl group described below.

[0066] For structural unit (A), when functional group (A) is a group having a conjugate anion of sulfonylimide group, it can be a structural unit represented by the following formula (A1).

[0067] [Chemical formula 1]

[0068]

[0069] (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, M +is an alkali metal ion, and * indicates the position where the structural unit (A1) is bonded to other structural units.)

[0070] As X, there is no particular limitation. It can be a hydrocarbon group, a group having a heteroatom, or can have a heterocycle. More specifically, as X, examples include a hydrocarbon group, a divalent group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are replaced by a linking group such as -O-, -S-, -C(=O)- or -C(=O)O-. It should be noted that in the case where there are a plurality of linking groups, the linking groups are not adjacent to each other. In addition, the above divalent group can have a substituent that replaces a hydrogen atom bonded to a carbon atom. As the substituent, it can be a monovalent substituent, and examples include a halogen atom. As the above hydrocarbon group, there is no particular limitation, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it can be any of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. X can be bonded to one or both of the nitrogen atom of the maleimide group and the sulfur atom of the sulfonyl group through a carbon atom possessed by X.)

[0071] The number of carbon atoms possessed by X can be 1 to 15, can be 2 to 10, and can be 3 to 8. X can 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, and an electron-withdrawing group can be bonded to the carbon atom that is a ring member of the carbocyclic ring. The hydrocarbon group of 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 a halogen atom such as a fluorine atom, and more preferably a phenylene group or a substituted phenylene group substituted by an alkyl group, a halogen atom, an electron-withdrawing group, etc. As the electron-withdrawing group, examples include a halogen atom, a sulfonic acid group or its salt, a sulfonate, a nitro group, and a nitrile group.)

[0072] In formula (A1), when Y is a monovalent organic group, there is no particular limitation on this organic group, and it may be a hydrocarbon group, a group having a heteroatom, or may also have a heterocycle. More specifically, examples of Y include a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are replaced by a linking group such as -O-, -S-, -C(=O)- or -C(=O)O-, etc. monovalent groups. It should be noted that when there are multiple linking groups, the linking groups are not adjacent to each other. In addition, the above monovalent group may have a substituent that replaces the hydrogen atom bonded to the carbon atom. As the substituent, it may be a monovalent substituent, for example, a halogen atom, etc. There is no particular limitation on the above hydrocarbon group, and it may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it may be any of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0073] The number of carbon atoms that Y has may be 1 to 15, may be 1 to 10, may be 1 to 8, may be 1 to 5, or may be 1 to 3. The hydrocarbon group of Y is preferably a phenyl group, an alkyl group having 1 to 5 carbon atoms, or a group obtained by substituting part or all of the hydrogen atoms bonded to the carbon atoms of these groups with a halogen atom such as a fluorine atom, more preferably a fluoroalkyl group having 1 to 5 carbon atoms, and still more preferably a fluoroalkyl group having 1 to 3 carbon atoms such as a trifluoromethyl group. The fluoroalkyl group may be a perfluoroalkyl group. When Y is a halogen atom, as the halogen atom, a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred.

[0074] In formula (A1), M + is preferably a lithium ion (Li + ), a sodium ion (Na + ), or a potassium ion (K + ), and more preferably a lithium ion. M + may contain 2 or 3 kinds of ions among Li + , Na + , and K + , but preferably contains substantially only a single ion.

[0075] The group having a conjugated anion with a sulfonic acid group is a group having a group obtained by substituting the hydrogen atom of the sulfonic acid group with an alkali metal (that is, an -SO 3 M group with M as the alkali metal, also called an alkali metalated sulfonic acid group).

[0076] The group having a conjugated anion with a carboxylic acid group is a group having a group obtained by substituting the hydrogen atom of the carboxylic acid group with an alkali metal (that is, a -COOM group with M as the alkali metal, an alkali metalated carboxylic acid group).

[0077] A group having a conjugated anion with a phenolic hydroxyl group is a group having a group obtained by alkali metalizing a hydroxyl group directly bonded to an aromatic ring (i.e., a phenolic hydroxyl group (-OH)) (i.e., an -OM group with M as an alkali metal).

[0078] The structural unit (A) can be a structural unit represented by the following formula (A2).

[0079] [Chemical formula 2]

[0080]

[0081] (In formula (A2), Y 2 is a group having an alkali metalized sulfonimide group, a group having an alkali metalized carboxyl group, a group having an alkali metalized phenolic hydroxyl group, or a group having an alkali metalized sulfonic acid group, and * represents the bonding position of the structural unit (A2) with other structural units. R 15 ~R 17 are each independently a hydrogen atom or a monovalent substituent, or R 16 is a hydrogen atom or a monovalent substituent, and R 15 and R 17 together form a divalent substituent.)

[0082] R 15 ~R 17 can be one or more hydrogen atoms, or all can be hydrogen atoms.

[0083] When R 15 ~R 17 are monovalent substituents, the monovalent substituents can be monovalent organic groups. The number of carbon atoms of the organic group can be 1 to 20, can be 1 to 15, can be 1 to 10, can be 1 to 5, can be 1 to 3. Examples of the organic group include hydrocarbon groups, groups having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are replaced by linking groups such as -O-, -S-, -C(=O)-, or -C(=O)O-, and other monovalent substituents such as groups having a heterocycle. In addition, the above monovalent substituents can have substituents that replace hydrogen atoms bonded to carbon atoms. Examples of the substituents include halogen atoms. The hydrocarbon group is not particularly limited and can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group can be any of a linear 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. Examples of the hydrocarbon group include methyl, ethyl, propyl, phenyl, etc.

[0084] Regarding R 15 ~R 17, the monovalent substituent may have an electron-withdrawing group or may be an electron-withdrawing group itself. The electron-withdrawing group may be bonded to the above monovalent organic group, and the above monovalent organic group may be an electron-withdrawing group. Examples of the electron-withdrawing group include a halogen atom, a sulfonic acid group or its salt, a sulfonate, a nitro group, a nitrile group, etc. As the halogen atom, any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be used.

[0085] In R 15 and R 17 When they together form a divalent organic group, the number of carbon atoms in the divalent organic group may be 1 to 20, may be 1 to 15, may be 1 to 10, may be 1 to 5, or may be 1 to 3. Examples of the organic group include a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are replaced by a linking group such as -O-, -S-, -C(=O)-, or -C(=O)O-, and a divalent substituent such as a group having a heterocycle. In addition, the above divalent organic group may have a substituent that replaces a hydrogen atom bonded to a carbon atom. Examples of the substituent include a halogen atom, etc. The above hydrocarbon group is not particularly limited and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, any one of a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, and a cyclic hydrocarbon group may be used. 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 propylene group, a butylene group, etc.

[0086] When Y 2 is a group having a phenolic hydroxyl group, Y 2 may be a group represented by any one of the following formulas (A21) to (A26).

[0087] [Chemical formula 3]

[0088]

[0089] (In formula (A21), at least one of the R A groups is -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), at least one of the R B groups is -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), at least one of the R C groups is -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), at least one of the R D groups is -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), RE At least one of the groups is an -OM group, and the rest are hydrogen atoms or monovalent substituents. M is an alkali metal element and can be Li, Na, or K. In formula (A26), R F At least one of the groups is an -OM group, and the rest are hydrogen atoms or monovalent substituents. M is an alkali metal element and can be Li, Na, or K.)

[0090] When the polymer has a functional group of formula (A21), in the benzene ring of formula (A21), from the bonding site of the functional group of formula (A21) to the polymer, the -OM group can be bonded to the para position. From the above bonding site, a hydrogen atom, an -OM group, a methyl group, an ethyl group, or a monovalent organic group having 1 to 20 carbon atoms (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) can be independently bonded at the meta position or the ortho position and the meta position respectively.)

[0091] The groups represented by formulas (A21) to (A26) can have 1 to 3 -OM groups, can have 1 or 2 -OM groups, and can have 1 -OM group.)

[0092] In formulas (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 its salt, a sulfonate, a nitro group, a nitrile group, etc. As the halogen atom, it can be any one of F, Cl, Br, and I.)

[0093] In addition, in formulas (A21) to (A26), the monovalent substituent can be an organic group having 1 to 20 carbon atoms. The number of carbon atoms of the organic group can be 1 to 15, can be 1 to 10, can be 1 to 5, and can be 1 to 3. Examples of the organic group include a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene) in the hydrocarbon group are replaced by a linking group such as -O-, -S-, -C(=O)-, or -C(=O)O-, and a monovalent group such as a group having a heterocycle. In addition, the above monovalent group can have a substituent that replaces a hydrogen atom bonded to a carbon atom. Examples of the substituent include a halogen atom, etc. The hydrocarbon group is not particularly limited and can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group can be any one of a linear 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. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, etc. In addition, the monovalent organic group itself can be an electron-withdrawing group.)

[0094] Y 2When it is a group having a conjugate anion of sulfonic acid, as Y 2 , the groups represented by the following formula (A3) can be exemplified.

[0095] [Chemical formula 4]

[0096]

[0097] (In formula (A3), R 19 is a covalent bond or a divalent organic group. M is an alkali metal element, and can be Li, Na or K, or can also be Li.)

[0098] In formula (A3), the number of carbon atoms of the divalent organic group can be 1 to 20, can be 1 to 15, can be 1 to 10, can be 1 to 5, can be 1 to 3. As the organic group, groups having a heterocycle such as a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are replaced by a linking group such as -O-, -S-, -C(=O)- or -C(=O)O-, etc. divalent substituents can be exemplified. In addition, the above divalent organic group may have a substituent that replaces a hydrogen atom bonded to a carbon atom. As the substituent, for example, a halogen atom etc. can be exemplified. As the above hydrocarbon group, there is no particular limitation, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it can be any of a linear 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, methylene, phenylene, etc. can be exemplified.

[0099] As the group having a conjugate anion of sulfonic acid, -SO 3 M, -CH 2 -SO 3 M, -C 6 H 4 -SO 3 M, etc. can be exemplified.

[0100] The functional group (B) is a functional group having the function of an anion receptor. An anion receptor is a chemical species that captures an anion by forming an electrostatic interaction, a hydrogen bond, an acid-base complex, etc. with the anion. The functional group (B) captures the counter anion of the metal salt in the metal salt and promotes the dissociation of the counter anion from the metal ion. As a result, the mobility of the metal ion increases. On the other hand, since the counter anion is captured by the polymer via the structural unit (B), the mobility of the counter anion decreases. It is considered that in the polymer having the functional group (B), the transport number of the metal ion is increased as a result. In addition, since the mobility of the metal ion increases, the polymer having the functional group (B) tends to have an increased metal ion conductivity.

[0101] Low-molecular chemical species (compounds, etc.) that function as anion receptors are known. As such substances, for example, the compounds described in U.S. Patent No. 6,022,643, U.S. Patent No. 5,705,689, U.S. Patent No. 6,120,941, etc. can be cited. The functional group (B) has a structure corresponding to the chemical species that functions as an anion receptor. It is considered that since this functional group is fixed to the polymer, unlike conventional low-molecular anion receptors, the captured anion can be fixed to the polymer structure, and its participation in the current generated by the anion migration can be more effectively suppressed.

[0102] 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 above functional group, and can be captured by interacting with the above functional group in a state of forming an ionic bond or ion pair with the metal ion.

[0103] The functional group having the function of an anion receptor can be Lewis acidic. In this case, the above functional group can accept the non-covalent electron pair of the anion and capture the anion by forming an acid-base complex. As such a functional group, a functional group having an electron-deficient atom can be cited. It should be noted that an electron-deficient atom refers to an atom that has formed a covalent bond with other atoms but the outermost electrons of this atom do not form an octet. As the electron-deficient atom, an atom belonging to Group 13 of the periodic table can be cited. More specifically, it can be at least one of aluminum and boron, or it can be boron.

[0104] In addition, as the functional group having the function of an anion receptor, a group having an azaether moiety can be used. The group having an azaether moiety is a group having an azaether compound as a substituent. The azaether compound is a compound obtained by substituting -O- of an ether compound with -NR E -(Here, R E is a hydrogen atom or an organic group). The azaether moiety can be either a chain-like azaether moiety or a cyclic azaether moiety, and can have both a chain-like azaether moiety and a cyclic azaether moiety. The group having an azaether moiety can have an electron-withdrawing group, for example, in a hydrocarbon moiety.

[0105] Hereinafter, the structural unit containing the functional group (B) will also be referred to as the structural unit (B). The functional group (B) can be included, for example, in the structural unit represented by the following formula (B).

[0106] [Chemical formula 5]

[0107]

[0108] (In formula (B), W is a functional group having the function of an anion receptor, R1 ~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.

[0109] The polymer having an ability to preferentially conduct metal ions may contain one or two or more structural units represented by formula (B).

[0110] 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.

[0111] R 1 ~R 3 When it is 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 a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene) in the hydrocarbon group are replaced by a connecting group of -O-, -S-, -C(=O)- or -C(=O)O-, and a group having a heterocyclic ring may be listed. 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 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 of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group may be any 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.

[0112] 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.

[0113] 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, and 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.

[0114] In R 1 and R2 When forming a divalent organic group together, the number of carbon atoms in the divalent organic group can be 1 to 20, can be 1 to 15, can be 1 to 10, can be 1 to 5, can be 1 to 3. As the organic group, there can be mentioned hydrocarbon groups, groups having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are substituted by a linking group such as -O-, -S-, -C(=O)- or -C(=O)O-, and divalent substituents such as groups having a heterocycle. In addition, the above divalent organic group can have a substituent that substitutes a hydrogen atom bonded to a carbon atom. As the substituent, for example, there can be mentioned a halogen atom. As the above hydrocarbon group, there is no particular limitation, and it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, it can be any of a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic hydrocarbon group. In addition, the hydrocarbon group can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. As the hydrocarbon group, there can be mentioned a propylene group, a butylene group, etc.

[0115] W preferably has a group represented by the following formula (B1).

[0116] [Chemical formula 6]

[0117]

[0118] (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 are a hydrogen atom, an -OH group, a halogen atom or a monovalent organic group, or together form a divalent organic group. R 6 and R 7 can be the same group or different groups.)

[0119] W B can be at least one of aluminum and boron, or can be boron.

[0120] In R 5In the case of a divalent organic group, the number of carbon atoms in the divalent organic group can be 1 to 20, can be 1 to 15, can be 1 to 10, can be 1 to 5, or can be 1 to 3. As the organic group, monovalent substituents such as a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are substituted with a linking group such as -O-, -S-, -C(=O)-, or -C(=O)O-, and a group having a heterocycle can be mentioned. In addition, the above divalent organic group may have a substituent that substitutes a hydrogen atom bonded to a carbon atom. The substituent may be an electron-withdrawing group. As the electron-withdrawing group, a halogen atom, a sulfonic acid group or its salt, a sulfonate, a nitro group, a nitrile group, etc. can be mentioned. As the halogen atom, any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be used. R 5 can be a hydrocarbon group, a halogen-substituted hydrocarbon group, or a group in which a hydrocarbon group or a halogen-substituted hydrocarbon group is bonded to W B via an ether bond. The halogen-substituted hydrocarbon group can be a group obtained by substituting part or all of the hydrogen atoms of the hydrocarbon group with halogen atoms, and can be a partially fluorinated hydrocarbon group or a perfluorinated hydrocarbon group. R 5 can be a covalent bond.

[0121] R 6 or R 7 When it is a halogen atom, it can be any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0122] When R 6 or R 7 is a monovalent organic group, the number of carbon atoms in the monovalent organic group can be 1 to 20, can be 1 to 15, can be 1 to 10, can be 1 to 5, or can be 1 to 3. As the organic group, monovalent substituents such as a hydrocarbon group, a group having a chemical structure in which one or more carbon atoms (methylene groups) in the hydrocarbon group are substituted with a linking group such as -O-, -S-, -C(=O)-, or -C(=O)O-, and a group having a heterocycle can be mentioned. In addition, the above monovalent organic group may have a substituent that substitutes a hydrogen atom bonded to a carbon atom. The substituent may be an electron-withdrawing group. As the electron-withdrawing group, a halogen atom, a sulfonic acid group or its salt, a sulfonate, a nitro group, a nitrile group, etc. can be mentioned. As the halogen atom, any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be used. R 6 or R 7 can be a hydrocarbon group, a halogen-substituted hydrocarbon group, or a group in which a hydrocarbon group or a halogen-substituted hydrocarbon group is bonded to W B via an ether bond. The halogen-substituted hydrocarbon group can be a group obtained by substituting part or all of the hydrogen atoms of the hydrocarbon group with halogen atoms, and can be a partially fluorinated hydrocarbon group or a perfluorinated hydrocarbon group.

[0123] W may be a group represented by the following formula (B1a) or a group represented by the following formula (B1b).

[0124] [Chemical formula 7]

[0125]

[0126] (In formula (B1a), X 1 and X 2 are each an oxygen atom (ether bond) or a covalent bond, R 11 and R 12 are each a halogen atom (except when X is an oxygen atom), a monovalent hydrocarbon group, a hydrogen atom, or a monovalent halogen-substituted hydrocarbon group, and may be a halogen atom, a monovalent hydrocarbon group, or a monovalent halogen-substituted hydrocarbon group. At least one of R 11 and R 12 may be a monovalent hydrocarbon group or a monovalent halogen-substituted hydrocarbon group. R 11 and R 12 may be the same group or different groups.)

[0127] [Chemical formula 8]

[0128]

[0129] (In formula (B1b), X 3 and X 4 are each an oxygen atom (ether bond) or a covalent bond, and R 13 is a divalent hydrocarbon group or a divalent halogen-substituted hydrocarbon group.)

[0130] In formula (B1a), when R 11 is a halogen atom, X 1 may be a covalent bond. When R 12 is a halogen atom, X 2 may be a covalent bond. When R 11 or R 12 is a monovalent hydrocarbon group or a monovalent halogen-substituted hydrocarbon group, the number of carbon atoms in the monovalent hydrocarbon group or the monovalent halogen-substituted hydrocarbon group may be 1 to 20, may be 1 to 15, may be 1 to 10, may be 1 to 5, or may be 1 to 3. The halogen-substituted hydrocarbon group may be a group obtained by substituting part or all of the hydrogen atoms of the hydrocarbon group with halogen atoms, and may be a partially fluorinated hydrocarbon group or a perfluorinated hydrocarbon group.)

[0131] R 11 and R 12 are each independently -F, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 6H 5 (phenyl), -C 6 H n F 5-n (n is an integer from 0 to 4, can be an integer from 0 to 3), -CF 3 、-CH 2 CF 3 、-CH 2 CF 3 CF 7 、-CH(CF 3 ) 2 、-C(CF 3 ) 2 -C 6 H 5 、-C(CF 3 ) 3 、-C 6 H n (CF 3 ) 5-n (n is an integer from 0 to 4, can be 1 or 2).

[0132] In formula (B1b), the divalent hydrocarbon group or the divalent halogen-substituted hydrocarbon group can have 1 to 20 carbon atoms, can have 1 to 15 carbon atoms, can have 2 to 10 carbon atoms, can have 3 to 8 carbon atoms. The halogen-substituted hydrocarbon group can be a group obtained by substituting part or all of the hydrogen atoms of the hydrocarbon group with halogen atoms, and can be a partially fluorinated hydrocarbon group or a perfluorinated hydrocarbon group.

[0133] R 13 Examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -C 5 H 10 -, -C 6 H 12 -, -C 7 H 14 -, -C 8 H 16 -, -C 9 H 18 -, -C 10 H 20 - etc., groups obtained by substituting part or all of their hydrogen atoms with fluorine, etc. More specifically, -C(CH 3 ) 2 -C(CH 3 ) 2 - is preferred.

[0134] The molar ratio m of the structural unit (B) to all the structural units contained in the polymer can be 0.2 to 0.8, can be 0.25 to 0.75, can be 0.3 to 0.7, can be 0.35 to 0.65, can be 0.4 to 0.6.

[0135] The molar ratio n of the structural unit (A) to all the structural units contained in the polymer can be 0.25 to 0.75, can be 0.3 to 0.7, can be 0.35 to 0.65, can be 0.4 to 0.6.

[0136] There is no problem as long as the sum of m and n is 1 or less, and it can be 0.95 or less. In addition, the sum of m and n can be 0.5 or more, can be 0.6 or more, can be 0.7 or more, can be 0.8 or more, can be 0.9 or more, can be 0.95 or more.

[0137] The content of the structural unit (A) relative to the total mass of the polymer can be 5 to 90% by mass, can be 20 to 80% by mass, can be 40 to 75% by mass, can be 55 to 70% by mass.

[0138] The content of the structural unit (B) relative to the total mass of the polymer can be 10 to 95% by mass, can be 15 to 95% by mass, can be 20 to 95% by mass, can be 20 to 80% by mass, can be 25 to 60% by mass, can be 30 to 45% by mass.

[0139] The sum of the contents of the structural unit (A) and the structural unit (B) relative to the total mass of the polymer can be 50% by mass or more, can be 70% by mass or more, can be 90% by mass or more, can be 95% by mass or more.

[0140] The polymer may contain a structural unit different from either the structural unit (A) or the structural unit (B), that is, the structural unit (C). As the structural unit (C), the structural unit represented by the following structural unit (C1), the structural unit represented by the structural unit (C2), etc. can be cited.

[0141] [Chemical formula 9]

[0142]

[0143] (In the formula (C1), R 21 ~R 24 are each independently a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 20 carbon atoms. * represents the position where the structural unit (C1) is bonded to other structural units.)

[0144] [Chemical formula 10]

[0145]

[0146] (In formula (C2), R 25 is a divalent organic group having 1 to 20 carbon atoms, R 26 and R 27 are each a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 25 can form a ring having an ethylene unit and an imide group of formula (C2) (succinimide ring or its N-derivative), or a ring having an anhydride group (succinic anhydride ring).)

[0147] R 21 to R 24 One or more of them can be a monovalent organic group. The monovalent organic group can be a group represented by -Z 1 -R 29 The number of carbon atoms each of R 21 to R 24 can have can be 1 to 40, can be 1 to 20, can be 2 to 15, or can be 4 to 13. Here, Z 1 is a divalent linking group and can be, for example, a covalent bond, -O-, -S-, -C(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)NR 38 -, or -NR 39 C(=O)-represented group. When Z 1 is a covalent bond, -O-, -S-, -C(=O)-, -C(=O)O-, or -OC(=O)-, R 29 is a hydrogen atom or a monovalent organic group. When Z is -C(=O)NR 38 -, R 29 , R 38 are each a hydrogen atom or a monovalent organic group, or R 29 and R 38 together form a ring. When it is -NR 39 C(=O)-, R 29 and R 39 are each independently a hydrogen atom or a monovalent organic group, or R 29 and R 39 together form a ring. As the monovalent organic group of R 29 , R 38 and R 39 can have 1 to 20 or 1 to 10 organic groups. When R 38 is a monovalent organic group, it can be a monovalent hydrocarbon group having 1 to 20 carbon atoms. When Z1 is a covalent bond or -C(=O)O-, R 29It may be a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When Z1 is a covalent bond and R 29 is a hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group. In addition, R 29 may be a monovalent organic group other than a hydrocarbon group or a hydrocarbon group having a ring structure. When Z 1 is -O-, it may be a monovalent organic group other than a group represented by W-H as an alkyl ether with W. When R 26 to R 28 are monovalent organic groups, examples of the monovalent organic groups include the same groups as those listed as examples of R 25 .

[0148] In addition, the structural unit (C) may contain a structural unit that is a precursor of the structural unit (A) (also referred to as a structural unit (Ap)). Examples of such a structural unit include unreacted structural units and intermediate structural units in the structural unit that is a precursor of the structural unit (A) (for example, a structural unit derived from a monomer (A2') described later) that cannot be converted into the structural unit (A). For example, a group that is the conjugate acid of the structural unit (A) (that is, a group obtained by replacing the alkali metal ion that is the counter cation of the structural unit (A) with H + ), and a group obtained by replacing the counter cation of the structural unit (A) with a cation other than an alkali metal ion, etc. Examples of the counter cation contained in the structural unit (Ap) include NH 4 + , organic ammonium cations, metal ions such as alkaline earth metal ions, etc. Relative to the total amount of the structural unit (A) and the structural unit (Ap), the polymer may contain 85 mol% or more, 90 mol% or more, or 95 mol% or more of the structural unit (A).

[0149] The polymer may contain structural units derived from hydrocarbon compounds having multiple ethylenically unsaturated groups such as butadiene and isoprene.

[0150] The polymer may have a structural unit derived from a crosslinking agent. Examples of the crosslinking agent include compounds having multiple ethylenically unsaturated groups in the molecule such as hexanediol diacrylate, pentaerythritol tetraacrylate, divinylbenzene, and triethylene glycol divinyl ether.

[0151] The number average molecular weight (Mn) of the polymer may be from 5,000 to 200,000, may be from 8,000 to 120,000, or may be from 10,000 to 100,000. The weight average molecular weight (Mw) of the polymer may be from 5,000 to 300,000, may be from 10,000 to 250,000, or may be from 20,000 to 100,000. The molecular weight distribution (Mw / Mn) of the polymer may be from 1.0 to 3.5, or may be from 1.3 to 2.7. The number average molecular weight and the weight average molecular weight of the polymer can be measured, for example, by gel permeation chromatography.

[0152] The content of the polymer in the electrode material may be 30% by mass or less, may be from 0.1 to 30% by mass, may be from 0.5 to 20% by mass, or may be from 1 to 10% by mass with respect to the total amount of the electrode material. The content of the polymer in the electrode material may be from 0.1 to 10% by mass, may be from 0.5 to 10% by mass, or may be from 1 to 10% by mass with respect to the total amount of the electrode material.

[0153] As a method for producing the polymer, there is no particular limitation, and for example, a method of polymerizing a monomer mixture containing at least one of a monomer having an anionic functional group ionized by an alkali metal ion 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 acceptor can be mentioned. The monomer may further contain a monomer (C') different from the monomer (A') and the monomer (B').

[0154] The monomer (A') and the monomer (B') may have an ethylenically unsaturated group. In this case, the monomer (A') and the monomer (B') can be polymerized by radical addition polymerization. In this case, the monomer can be polymerized in the presence of an initiator. That is, the polymerization reaction can be carried out in a polymerizable composition containing the monomer and the initiator.

[0155] The monomer (A') is a monomer that derives a structural unit (A) in the polymer. As the monomer (A'), the monomer (A1') represented by the following formula (A1'), the monomer (A2') represented by the formula (A2'), etc. can be mentioned.

[0156] [Chemical formula 11]

[0157]

[0158] (X, Y, and M in the formula (A1') + have the same meanings as those in the formula (A).)

[0159] [Chemical formula 12]

[0160]

[0161] (In formula (A2’), the meanings of R 15 ~R 17 are the same as those of R 15 ~R 17 in formula (A2). Y2’ is a group capable of derivatizing a phenolic hydroxyl group corresponding to the -OM group possessed by Y 2 in formula (A2), a group capable of derivatizing a sulfonic acid group corresponding to the -SO 2 M group possessed by Y 3 , a group capable of derivatizing an alkali metalated sulfonylimide group possessed by Y 2 , or a group capable of derivatizing a group having an alkali metalated carboxylic acid possessed by Y 2 .)

[0162] Y 2 ’ can be the same group as Y 2 , or a group that is a precursor of Y 2 . That is, Y 2 ’ is a group having a group capable of being converted to an -OM group or -SO 2 M group at the same position as the -OM group or -SO 3 M group possessed by the desired Y 3 .

[0163] As a group capable of derivatizing a phenolic hydroxyl group corresponding to the -OM group possessed by Y 2 , for example, a hydrolyzable group can be cited. A phenolic hydroxyl group can be introduced at the position corresponding to the -OM group possessed by Y 2 by hydrolyzing the hydrolyzable group. As the hydrolyzable group, for example, an alkoxide group or -OSi(R k ) 3 group (R k is a monovalent organic group such as a hydrocarbon group) can be cited. The phenolic hydroxyl group can be converted to an -OM group, for example, by reacting with an alkaline salt of an alkali metal such as MOH, M 2 CO 3 , MHCO 3 .

[0164] Similarly, as a group capable of derivatizing a sulfonic acid group corresponding to the -SO 2 M group possessed by Y 3 , for example, a sulfonic acid ester group, -SO 2 Cl group, etc., which can derivatize a sulfonic acid group (-SO 3 H), can be cited. The sulfonic acid group can be converted, for example, by reacting with an alkaline salt of an alkali metal such as MOH, M 2 CO 3 , MHCO 3, it reacts with salts of alkali metals such as alkali metal halides to be converted into -OM groups. Additionally, regarding the -SO 2 Cl group, it can also react with MOH to be converted into -SO 3 M group. When an excessive amount of MOH is used, most of the -SO 2 Cl groups can be converted into -SO 3 M groups. In this reaction, a part of the -SO 2 Cl groups may become -SO 3 H groups, but regarding the -SO 3 H groups, they can also react separately with an alkali containing M to form -SO 3 M groups. Additionally, Y 2 ’ can be a group that has the same anionic part as Y 2 and forms a salt with a cation other than an alkali metal ion. At this time, by performing a cation exchange reaction on the obtained polymer, the structural unit (A2) can be derived. The reaction rate of Y2’ (the proportion of Y 2 ’ that is converted into Y 2 ) can be 85 mol% or more, 90 mol% or more, or 95 mol% or more.

[0165] As a group capable of deriving an alkali metalated sulfonylimide group, a group having an alkali metalated sulfonylimide group or a group having a group as its conjugate acid can be cited. As a group capable of deriving a group having an alkali metalated carboxylic acid, a group having a carboxyl group (-COOH) or its salt can be used. When the monomer (A2’) has a group capable of deriving a group having an alkali metalated carboxylic acid, the monomer (A2’) can be an unsaturated fatty acid or its salt. The unsaturated fatty acid can have one or more carboxyl groups or their salts.

[0166] The monomer (B’) is a monomer that derives the structural unit (B) in the polymer. As the monomer (B’), the monomer (B’) represented by the following formula (B’) can be cited.

[0167] [Chemical formula 13]

[0168]

[0169] (In the formula, the meanings of R 1 to R 3 and W are the same as those of R 1 to R 3 and W in formula (B).)

[0170] 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-cyclohexanenitrile) (ACHN, V-40), dimethyl-2,2-azobisisobutyrate (MAIB), etc.; organic peroxides such as benzoyl peroxide, di-(8,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, di(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.

[0171] The electrode material of the present embodiment can further contain a binder resin (adhesive resin), a conductive additive, etc. There is no particular limitation on the binder resin, and fluororesins, synthetic rubbers, etc. can be cited. As the fluororesin, a resin having a carbon chain as the main chain is preferred. The carbon chain can be formed by radical polymerization of an ethylenically unsaturated group. As the fluororesin, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (PVDF), etc. can be cited. As the synthetic rubber, SBR (styrene-butadiene rubber), etc. can be cited. The content of the binder resin in the electrode material can be 0.5 to 10% by mass, or can be 1 to 7% by mass.

[0172] As the conductive additive, carbon nanotubes, natural graphite (such as flake graphite), artificial graphite and other graphite-based materials; acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal cracking carbon black and other carbon black-based materials; carbon fibers; and other carbon materials can be cited. The carbon nanotubes can be either single-layer or multi-layer, or can be multi-layer. The average length of the carbon nanotubes can be 1 μm or more, or can be 5 μm or more. The conductivity of the carbon nanotubes can be metallic. The average diameter of the carbon nanotubes can be 0.4 nm to 100 nm. The BET specific surface area of the carbon nanotubes can be 400 m 2 / g or less. The G / D ratio of the carbon nanotubes can be 10 or less. The tensile strength of the carbon nanotubes can be 50 to 70 MPa. The content of the conductive additive in the electrode material can be 0.05 to 15% by mass, can be 0.1 to 10% by mass, can be 0.5 to 10% by mass, can be 1 to 7% by mass.

[0173] The electrode material of the present embodiment can be used as a composition for forming a positive electrode or a negative electrode. The electrode material of the present embodiment can be used as a composition for forming an electrode of an electrochemical device such as a capacitor or a battery. Examples of the battery include batteries that charge and discharge through the migration of alkali metal ions, such as lithium ion batteries and sodium ion batteries. The battery can be a primary battery, a secondary battery, or a solid battery.

[0174] 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. At least one of the positive electrode and the negative electrode may include the electrode material of the present embodiment. The positive electrode may be a positive electrode in which a layer containing a positive electrode material is formed on a current collector. In addition, the negative electrode may be a negative electrode in which a layer containing a negative electrode material is formed on a current collector.

[0175] The electrolyte is not particularly limited. For example, it may be an electrolyte containing a polymer having the ability to preferentially conduct the above metal ions. The electrolyte may further include an ion-conductive inorganic solid electrolyte, an organic solvent, an ionic liquid, etc. The ion-conductive inorganic solid electrolyte is not particularly limited and may be an oxide (oxide-based solid electrolyte), a sulfide (sulfide-based solid electrolyte), a hydride (hydride-based solid electrolyte), or a halide (halide-based solid electrolyte). The ion-conductive inorganic solid electrolyte may contain at least one of an alkali metal element and an alkaline earth metal element, or may contain an alkali metal element. In the electrolyte composition, the polymer may be swollen by the organic solvent. The content of the organic solvent in the electrolyte composition or the electrolyte may be 10 to 1000 parts by mass, 50 to 800 parts by mass, or 100 to 500 parts by mass with respect to 100 parts by mass of the polymer having the ability to preferentially conduct metal ions.

[0176] The battery may have a separator. The separator may be a porous material or a resinous porous material. Specifically, porous polyolefin membranes, porous ceramic membranes, etc. may be cited.

[0177] Examples

[0178] [Manufacture of Polymer Having the Ability to Preferentially Conduct Metal Ions]

[0179] As described below, a copolymer of monomer A1 represented by the following formula and styrene is manufactured.

[0180] [Chemical Formula 14]

[0181]

[0182] First, monomer A1 is manufactured as follows.

[0183] (Synthesis of Monomer A1)

[0184] Under a 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., Inc.). 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 successively added to this solution, and the mixture was 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 then washed with dichloromethane (manufactured by Kanto Chemical Co., Inc.) to obtain Intermediate 1. The yield was 97.1%.

[0185] · Structural formula of Intermediate 1:

[0186] [Chemical formula 15]

[0187]

[0188] Under a nitrogen atmosphere, 5% hydrochloric acid (22.5 mL) was added to Intermediate 1 (15 mmol, 5.28 g), and the mixture was stirred at 90 °C for 2 hours. After cooling to room temperature, according to the confirmation with pH test paper etc., an aqueous lithium hydroxide solution was added until the pH reached 7 or above, and then a solid was obtained by drying under reduced pressure. The obtained solid was extracted with an acetonitrile solution, and Intermediate 2 was obtained by drying under reduced pressure. Based on the raw materials of the above Intermediate 1, the yield was 92.6%.

[0189] · Structural formula of Intermediate 2:

[0190] [Chemical formula 16]

[0191]

[0192] Under a nitrogen atmosphere, 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., Inc.). A solution of Intermediate 2 (13.2 mmol, 4.09 g) prepared under a nitrogen atmosphere in dehydrated tetrahydrofuran (26.4 mL, manufactured by Kanto Chemical Co., Inc.) was added dropwise to this solution, and the mixture was 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.

[0193] · Structural formula of Intermediate 3:

[0194] [Chemical formula 17]

[0195]

[0196] Under a nitrogen atmosphere, a solid containing Intermediate 3 (14.0 mmol, 5.70 g) and an aqueous solution of sodium acetate (13.3 mmol, 1.09 g, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to acetic anhydride (12.3 mL, manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 70 °C for 3 hours. The entire amount of the reaction solution was dropped into an excess of diethyl ether (manufactured by Kanto Chemical Co., Inc.) 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., Inc.), and monomer A1 was obtained by drying under reduced pressure. The yield in all steps was 72.8%.

[0197] 3.121 g of monomer A1, 0.833 g of styrene, and 57.5 mg of AIBN were dissolved in 70 mL of dehydrated acetonitrile, and tetralin as an internal standard was added. While confirming the monomer consumption rate, the reaction was carried out at 60 °C for 24 hours under a nitrogen atmosphere. The polymerization solution was dialyzed in acetonitrile and dried under vacuum at 120 °C to obtain 3.50 g of a polymer (yield 89%). The monomer feed ratio was A1:styrene = 54:46. The monomer feed ratio was calculated from the 1 1H-NMR of the copolymer. It should be noted that as styrene, a commercially available reagent with a purity > 98% manufactured by Aldrich was sealed, dried overnight, and CaH 2 was added, followed by distillation under reduced pressure to increase the purity before use. 2

[0198] The number-average molecular weight Mn of the copolymer = 9.3×10 4 , the weight-average molecular weight Mw = 3.0×10 5 , and the molecular weight distribution Mw / Mn = 3.19.

[0199] [Manufacture of Cathode Material]

[0200] (Example 1)

[0201] LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 as the cathode active material, the polymer having the ability to preferentially conduct metal ions manufactured as described above, acetylene black, and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 87:4.3:4.3:4.3 to obtain a cathode material. The details of the cathode active material are as follows.

[0202] Nominal: LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2

[0203] Composition analysis by ICP: Li​1.05 Ni 0.33 Co 0.33 Mn 0.34 O 2

[0204] Crystal structure: R-3m

[0205] Average particle size: 10 μm

[0206] (Example 1’)

[0207] Mix LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 which is used as the positive electrode active material, the polymer having the ability to preferentially conduct metal ions manufactured as described above, carbon nanotubes, and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) in a mass ratio of 93.5:3:0.5:3 to obtain a positive electrode material. In addition, the carbon nanotubes are multi-layered with an average diameter of 10 nm.

[0208] (Example 1”)

[0209] Mix LiFePO 4 (LFP), which is used as the positive electrode active material, the polymer having the ability to preferentially conduct metal ions manufactured as described above, the above-mentioned carbon nanotubes, and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) in a mass ratio of 93.5:3:0.5:3 to obtain a positive electrode material. The details of the positive electrode active material are as described below.

[0210] Nominal: LiFePO 4

[0211] Crystal structure: Pnma

[0212] Average particle size: 1.0 μm

[0213] (Comparative Example 1)

[0214] Mix the positive electrode active material LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 with a mixture of poly(ethylene oxide) (average Mv 600,000, powder) manufactured by Aldrich and lithium bis(fluorosulfonyl)imide (LiFSI) manufactured by KISHIDA CHEMICAL CO., LTD. (molar ratio of O atom:Li atom = 20:1), acetylene black, and polyvinylidene fluoride (PVDF) in a mass ratio of 87:4.3:4.3:4.3 to obtain a positive electrode material.

[0215] [Manufacture of Electrolyte]

[0216] Manufacture electrolyte composition 1 containing a polymer with the ability to preferentially conduct metal ions manufactured as described above, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and an organic solvent (ethylene carbonate:propylene carbonate = 1:1 (volume ratio)) (KISHIDA CHEMICAL CO., LTD.) in a mass ratio of 17:17:66.

[0217] In addition, manufacture electrolyte composition 2 with the ratio of the above electrolyte composition changed to a mass ratio of 23:11:44.

[0218] [Charge and Discharge Test]

[0219] Inside a glove box, under a dry argon atmosphere, use the positive electrode materials of Example 1 and Comparative Example 1 above and the above electrolyte composition to assemble an evaluation battery of coin-type battery CR2032. Specifically, stack each layer in the following order inside the evaluation battery to produce a test laminate.

[0220] (Positive electrode / electrolyte composition / lithium)

[0221] Use the above evaluation battery to perform charge and discharge measurements for 5 cycles in the range of 2.5 - 4.3 V (vs. Li / Li + ) to measure the cycle retention rate after 5 cycles.

[0222] Figure 1 It is a graph showing the results of the charge and discharge test of the battery using the positive electrode material and electrolyte composition 1 of Example 1. In addition, Figure 2 shows the results of the charge and discharge test of the battery using the positive electrode material and electrolyte composition 1 of Comparative Example 1. It can be seen that in Example 1, even after repeated cycling, the capacity did not decrease, but in Comparative Example 1, the capacity decreased significantly with repeated cycling. For the battery using the positive electrode material of Example 1, the cycle capacity retention rate after 5 cycles was 99%. On the other hand, for the battery using the positive electrode material of Comparative Example 1, the cycle capacity retention rate after 5 cycles was 75%.

[0223] In addition, similarly, batteries are manufactured using the positive electrode materials of Example 1' or Example 1" and electrolyte composition 2, and charge and discharge tests are performed. Figure 7 It is a graph showing the results of the charge and discharge test of the battery using the positive electrode material and electrolyte composition 2 of Example 1'. Figure 8 It is a graph showing the results of the charge and discharge test of the battery using the positive electrode material and electrolyte composition 2 of Example 1". The cycle capacity retention rates after 5 cycles are all 97% or more.

[0224] In addition,Figure 3 It is a differential capacity curve of the charge-discharge test of the battery using the positive electrode material of Example 1 and the electrolyte composition 1. In addition, Figure 4 It is a differential capacity curve of the charge-discharge test of the battery using the positive electrode material of Comparative Example 1 and the electrolyte composition 1. Figure 3 and Figure 4 The differential capacity curves are obtained by regarding the capacity as a function of voltage and differentiating with voltage in the charging side curve of the charge-discharge curve in the third cycle. In Figure 3 and Figure 4 , the upwardly convex curve graph corresponds to the charging curve, and the downwardly convex curve graph corresponds to the discharging curve. It was confirmed that: in Example 1, a beautiful curve could be depicted, but in Comparative Example 1, noise considered to be from side reactions other than the electrode reaction was generated.

[0225] [Manufacture of negative electrode material]

[0226] (Example 2)

[0227] Lithium titanate (Li 4 Ti 5 O 12 ) as the negative electrode active material, the polymer having the ability to preferentially conduct metal ions manufactured as described above, acetylene black, and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 87:4.3:4.3:4.3 to obtain a negative electrode material. The details of the negative electrode active material are as described below.

[0228] Li 4 Ti 5 O 12

[0229] Crystal structure: Spinel structure

[0230] Average particle size: 10 μm

[0231] [Charge-discharge test]

[0232] [Evaluation using a half cell]

[0233] Except for using the negative electrode material of Example 2 for the positive electrode, an evaluation battery (half cell) of a coin-type battery CR2032 was produced in the same manner as in Example 1. Using the above evaluation battery, charge-discharge measurement was performed for 10 cycles in the range of 1 - 3 V (vs. Li / Li + ). Figure 5 It is a graph showing the results of the charge-discharge test of the half cell using the negative electrode material of Example 2.

[0234] [Evaluation using a full cell]

[0235] Except for using the negative electrode material of Example 2 for the negative electrode, an evaluation battery (full battery) of a coin-type battery CR2032 was fabricated in the same manner as in Example 1 using lithium as the negative electrode. Using the above evaluation battery, charge-discharge measurements were performed for 10 cycles in the range of 0.5 to 3.3 V (vs. Li / Li + ). Figure 6 FIG. shows the results of charge-discharge tests of full batteries using the electrode materials of Examples 1 and 2.

[0236] <Peeling strength of the positive electrode material>

[0237] 65% by volume of LiNi as the positive electrode active material 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 and 14.6% by volume of acetylene black and 20.3% by volume of a binder were mixed to fabricate a positive electrode material. In each of the examples and comparative examples, the following substances were used as the binder.

[0238] Example 3: Use the above polymer having the ability to preferentially conduct metal ions.

[0239] Example 4: Use the above polymer having the ability to preferentially conduct metal ions and PVDF in a volume ratio of 1:1.

[0240] Comparative Example 3: Use LATP powder (manufactured by OHARA INC., LICGC PW-01 powder).

[0241] Comparative Example 4: Use the above LATP powder and PVDF in a volume ratio of 1:1.

[0242] Each positive electrode material described in Table 1 was formed into a sheet on a 20-μm aluminum foil (current collector), punched into a circular shape, and a laminate was fabricated. After a commercially available tape was adhered to the entire surface of the positive electrode material in the circular laminate in such a manner that no bubbles were present, the tape was peeled off. The thickness of the laminate before the tape was adhered to the positive electrode material and the thickness after the tape was peeled off were measured, and (thickness after tape peeling) / (thickness before tape adhesion) was taken as the residual ratio. The results are shown in Table 1. In Table 1, the polymer having the ability to preferentially conduct the above metal ions and the LATP powder are collectively referred to as ion conductors.

[0243] Table 1

[0244] Positive electrode material Ionic conductor / positive electrode material (volume%) Positive electrode material residue rate (%) Example 3 20.3 95 Example 4 10.2 90 Comparative Example 3 20.3 78 Comparative Example 4 10.2 80

[0245] <Peeling strength of the negative electrode material>

[0246] 65% by volume of carbon-coated Li as the negative electrode active material 4 Ti5 O 12 、 14.6 vol% acetylene black and 20.3 vol% binder are mixed to produce the negative electrode material. In each of the examples and comparative examples, the following substances are used as the binder.

[0247] Example 5: The polymer having the ability to preferentially conduct metal ions as described above is used.

[0248] Example 6: The polymer having the ability to preferentially conduct metal ions as described above and PVDF are used in a volume ratio of 1:1.

[0249] Comparative Example 5: The above-mentioned LATP powder is used.

[0250] Comparative Example 6: The above-mentioned LATP powder and PVDF are used in a volume ratio of 1:1.

[0251] Except for using the above-mentioned various negative electrode materials instead of the positive electrode material, a laminate containing the negative electrode material is produced in the same manner as the laminate containing the positive electrode material, and a peel test is performed. The results are shown in Table 2.

[0252] Table 2

[0253] Negative electrode material Ionic conductor / negative electrode material (volume%) Negative electrode material residue rate (%) Example 5 20.3 91 Example 6 10.2 91 Comparative Example 5 20.3 50 Comparative Example 6 10.2 89

[0254] <Measurement of lithium ion transference number>

[0255] (Reference Example 1)

[0256] An electrolyte composition is manufactured that contains the polymer having the ability to preferentially conduct metal ions as manufactured above, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and an organic solvent (ethylene carbonate: propylene carbonate = 1:1 (volume ratio)) (KISHID ACHEMICAL Co., Ltd.) in a mass ratio of 17:17:66.

[0257] (Reference Comparative Example 1)

[0258] Comparative Example: An electrolyte composition is manufactured that contains a mixture of poly(ethylene oxide) (average Mv 600,000, powder) manufactured by Aldrich and lithium bis(fluorosulfonyl)imide (LiFSI) manufactured by Kanto Chemical Co., Inc. (molar ratio of O atom: Li atom = 20:1).

[0259] The transference number of the above-mentioned electrolyte composition is measured by the following method. The results are shown in Table 3.

[0260] Lithium ion transference number:

[0261] An evaluation cell of the coin-type lithium 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 fabricate a test laminate. (Lithium / electrolyte composition / lithium)

[0262] The method for measuring the lithium ion transference number was introduced in Polymer, 28, 2324 (1987). That is, at room temperature (25 °C), a voltage of 10 mV was applied to the test laminate, and the initial current value (I 0 ) and the steady-state current value (I ss ) were measured. Furthermore, the interfacial resistance measurement value R 0 before the voltage application and the interfacial resistance measurement value R SS after the voltage application were obtained by the complex impedance method. Then, the obtained values were substituted into the following formula to calculate the lithium ion transference number (t Li+ ). V in the formula is the applied voltage.

[0263] t Li+ = I ss (V - I 0 R 0 ) / I 0 (V - I SS R SS )

[0264] Table 3

[0265] Lithium ion transference number (-) Reference Example 1 0.91 Reference Comparative Example 1 0.40

Claims

1. An electrode material containing an electrode active material and a polymer having the ability to preferentially conduct metal ions, wherein the volume ratio of the polymer to the total volume of the electrode active material and the polymer is 0.01 to 0.

65.

2. A positive electrode material containing a positive electrode active material and a polymer having the ability to preferentially conduct metal ions, wherein the volume ratio of the polymer to the total volume of the positive electrode active material and the polymer is 0.03 to 0.

50.

3. A positive electrode material containing a positive electrode active material and a polymer having the ability to preferentially conduct metal ions, wherein the mass ratio of the polymer to the total mass of the positive electrode active material and the polymer is 0.01 to 0.

30.

4. The positive electrode material according to claim 2 or 3, wherein, the polymer has at least one of an anionic functional group having an alkali metal ion as a counter cation and a functional group having an anion capturing ability.

5. The positive electrode material according to claim 2 or 3, wherein, it further contains a binder resin.

6. The positive electrode material according to claim 2 or 3, wherein, the positive electrode active material contains an alkali metal composite oxide containing nickel.

7. A positive electrode comprising the positive electrode material according to claim 2 or 3.

8. A battery comprising the positive electrode according to claim 7.

9. A negative electrode material containing a negative electrode active material and a polymer having the ability to preferentially conduct metal ions, wherein the volume ratio of the polymer to the total volume of the negative electrode active material and the polymer is 0.03 to 0.

65.

10. A negative electrode material containing a negative electrode active material and a polymer having the ability to preferentially conduct metal ions, wherein the mass ratio of the polymer to the total mass of the negative electrode active material and the polymer is 0.01 to 0.

32.

11. The negative electrode material according to claim 9 or 10, wherein, the polymer has at least one of an anionic functional group having an alkali metal ion as a counter cation and a functional group having an anion capturing ability.

12. The negative electrode material according to claim 9 or 10, which further contains a binder resin.

13. The negative electrode material according to claim 9 or 10, wherein, the negative electrode active material contains at least one selected from oxides containing titanium, active materials containing silicon, and carbon materials.

14. A negative electrode comprising the negative electrode material according to claim 9 or 10.

15. A battery comprising the negative electrode according to claim 14.

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