JP2005285332A - Polymer solid electrolyte battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer solid electrolyte battery excellent in cycle characteristics by using a polymer solid electrolyte with high ionic conductivity, high thermal characteristics, and high physical characteristics. <P>SOLUTION: The polymer solid electrolyte battery comprises the polymer solid electrolyte and electrodes, the polymer solid electrolyte is a crosslinked body formed by the reaction of a copolymer having a repeating unit induced from methoxypolyethylene methacrylate or the like and a repeating unit having a crosslinked point induced from 2-hydroxyethyl acrilate or the like and a crosslinker, and the electrode contains an electrode active material and a copolymer having a block chain A11 having a repeating unit induced from methoxypolyethylenegrycol methacrylate or the like, a block chain B11 having a repeating unit induced from styrene or the like, and a block chain C11 in the arrangement in the order of B11, A11, and C11. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer solid electrolyte battery particularly useful as a secondary battery.

A method for producing a positive electrode for a lithium secondary battery as a method for improving the charge / discharge cycle characteristics of a positive electrode of a solid-state lithium secondary battery, comprising: (1) 3V class Mn oxide, conductive additive, binder and organic A first step of forming an electrode layer comprising a mixture containing a solvent on the current collector, (2) a second step of obtaining an electrode plate by removing the organic solvent by drying the electrode layer, and (3) an electrode plate There is known a method for producing a composite positive electrode for a solid-state lithium secondary battery, comprising a third step of press molding and (4) a fourth step of impregnating an electrode layer with a lithium ion conductive polymer electrolyte. . (See Patent Document 1)
JP 2002-157998 A

  However, there is a problem that sufficient conductivity may not be obtained depending on the combination of the lithium ion conductive polymer electrolyte impregnated in the electrode and the polymer used in the electrolyte.

  An object of the present invention is to provide a battery having excellent cycle characteristics using a polymer solid electrolyte having excellent ion conductivity, thermal characteristics, and physical characteristics.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a solid electrolyte composed of a cross-linked copolymer having an ion conductive site and an electrolyte salt, and 50% or more of the copolymer and its constituent units. The inventors have found that the above-mentioned problems can be solved by combining electrodes containing copolymers having the same number, and have completed the present invention.

That is, the present invention
(1) In a battery comprising a polymer solid electrolyte and an electrode, the polymer solid electrolyte is represented by the formula (I)

(In the formula, R _{1 to} R ₃ each independently represents a hydrogen atom or a C 1-10 hydrocarbon group, and R ₁ and R ₃ may combine to form a ring; R _4a and R _4b Each independently represents a hydrogen atom or a methyl group, R ₅ represents a hydrogen atom, a hydrocarbon group, an acyl group or a silyl group, m represents an integer of 1 to 100, and m represents 2 In the above case, R _4a and R _4b may be the same or different.), And the formula (II)

(Wherein, R ₆ and R ₈ are each independently, represent a hydrogen atom or a C1~C10 hydrocarbon group,, R ₆ and R ₈ may be bonded to form a ring, R ₇ is , Hydrogen atom, C1-C10 hydrocarbon group, hydroxyl group, hydrocarbon oxy group, carboxyl group, acid anhydride group, amino group, ester group, or hydroxyl group, carboxyl group, epoxy group, acid anhydride group, and amino group Represents an organic group having at least one functional group selected from the group consisting of: R ₉ represents at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. A cross-linked product obtained by the reaction of a copolymer having a repeating unit represented by the formula (XX) with a cross-linking agent, the electrode comprising an electrode active material, and the formula (XX)

(Wherein R _{1a to} R _3a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R _1a and R _3a may combine to form a ring, R _4a1 , R _4b1 independently represents a hydrogen atom or a methyl group, R _5a represents a hydrogen atom, a hydrocarbon group, an acyl group, or a silyl group, m1 represents any integer of 2 to 100, R _4a1 and _R4b1 may be the same or different from each other.) A block chain A11 having a repeating unit represented by formula (XXI):

(Wherein R _{6a to} R _8a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R _9a represents an aryl group), a block chain B11 having a repeating unit represented by: And a battery characterized in that the block chain C11 is an electrode comprising a copolymer having a sequence of B11, A11, C11 in order,
(2) The battery according to (1), wherein the crosslinking agent is used in a range of 0.01 to 2 mol with respect to 1 mol of the repeating unit represented by the formula (II).
(3) The battery according to (1), wherein the crosslinking agent is used in a range of 0.1 to 1 mol with respect to 1 mol of the repeating unit represented by the formula (II).
(4) The copolymer having repeating units represented by formula (I) and formula (II) contains 5 mol or more of repeating units represented by formula (I) (1) to (1) 3) The battery according to any one of
(5) The copolymer having repeating units represented by formula (I) and formula (II) contains 5 mol or more of repeating units represented by formula (II) (1) to (1) 4) the battery according to any one of
(6) The number of moles of the repeating unit represented by formula (I) is in the range of 5 to 99% with respect to the total number of moles of repeating units in the copolymer, and the repeating unit represented by formula (II) The battery according to any one of (1) to (5), wherein the number of moles is in the range of 1 to 95% with respect to the total number of moles of repeating units in the copolymer,
(7) The repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) are bonded by a block, as described in any one of (1) to (6) It relates to batteries.
(8) The copolymer having repeating units represented by formula (I) and formula (II) is further different from the formula (I) and formula (II) derived from the polymerizable unsaturated monomer. The battery according to any one of (1) to (7), comprising a unit,
(9) The repeating unit different from the formula (I) and the formula (II) derived from the polymerizable unsaturated monomer is represented by the formula (III)

(Wherein R _{10 to} R ₁₂ each independently represents a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group, and R ₁₃ represents an aryl group or a heteroaryl group) and formula (IV)

(Wherein, R ₁₄ to R ₁₆ each independently represent a hydrogen atom or a C1~10 hydrocarbon group,, R ₁₄ and R ₁₆ are taken together, may form a ring, R ₁₇ is (C1-12 represents an alkyl group, an aryl group, an alicyclic hydrocarbon group, or a heterocyclic group.) (8), which is at least one repeating unit selected from repeating units represented by (8). The battery described,
(10) The battery according to (8) or (9), comprising 5 mol or more of a repeating unit different from the formula (I) and the formula (II) derived from a polymerizable unsaturated monomer,
(11) Repeating unit represented by formula (I), repeating unit represented by formula (II), and repeating unit different from formula (I) and formula (II) derived from a polymerizable unsaturated monomer Are connected by a block, The battery according to any one of (8) to (10),
(12) The total number of moles of repeating units different from the formula (I) and the formula (II) derived from the repeating unit represented by the formula (I) and the polymerizable unsaturated monomer is the total number of repeats in the copolymer. The number of moles of the repeating unit represented by the formula (II) is from 1 to 95% based on the total number of moles of repeating units in the copolymer. The battery according to any one of (8) to (11),
(13) The number of moles of the repeating unit represented by the formula (I) is in the range of 9.9 to 80% with respect to the total number of repeating unit moles in the copolymer, and is represented by the formula (II). The number of moles of the repeating unit is in the range of 0.1 to 50%, and the number of moles of the repeating unit different from the formula (I) and the formula (II) derived from the polymerizable unsaturated monomer is 19.9 to 90. % Of the battery according to any one of (8) to (12).
(14) A copolymer having a repeating unit represented by formula (I) and formula (II) is a block chain A having a repeating unit represented by formula (I), and a repeat represented by formula (II) A block chain B1 having a unit, a block chain B2 having a repeating unit represented by the formula (II) which may be the same as or different from the block chain B1, and a formula (III)

(Wherein R _{10 to} R ₁₂ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₁₃ represents an aryl group or a heteroaryl group). The block chain C1 and the block chain C2 having the repeating unit represented by the formula (III) which may be the same as or different from the block chain C1 are arranged in the order B1, C1, A, C2, B2. The battery according to any one of (9) to (13), which is a polymer,
(15) The battery according to (14), wherein the arrangement in the order of B1, C1, A, C2, and B2 is an array in which B1-C1-A-C2-B2 is combined.
(16) The repeating unit represented by the formula (II) is represented by the formula (IVA)

(Wherein R _{18 to} R ₂₀ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁₈ and R ₂₀ may be bonded to form a ring, and R ₂₁ represents C1 to C20) A C6 alkylene group, a C6 to C10 divalent aromatic hydrocarbon group, a C3 to C10 divalent alicyclic hydrocarbon group, or a divalent organic group in which these are combined.) (V)

(Wherein R _{22 to} R ₂₄ each independently represents a hydrogen atom or a C 1 to C 10 hydrocarbon group, and p represents an integer of 1 to 3), (VI)

(Wherein, R _181, R ₁₉₁ and R ₂₀₁ each independently represent a hydrogen atom or a C1~C10 hydrocarbon group, R ₁₈₁ and R ₂₀₁ may be combined to form a ring, R ₂₁₁ Represents a C1 to C6 alkylene group, a C6 to C10 divalent aromatic hydrocarbon group, a C3 to C10 divalent alicyclic hydrocarbon group, or a divalent organic group composed of these, and R ₂₁₂ represents a hydrogen atom. Or a C1-C4 alkyl group) or a repeating unit represented by formula (VII)

(Wherein R ₂₈₁ , R ₂₉₁ and R ₃₀₁ each independently represents a hydrogen atom or a C1-C10 hydrocarbon group, R ₂₈₁ and R ₃₀₁ may combine to form a ring, R ₃₁₁ Is a hydrogen atom or formula (VIII)

(Wherein, R ₄₁₁ represents a C1~C6 alkylene group, a divalent aromatic hydrocarbon group of C6-C10, 2 Ataiabura cyclic hydrocarbon group C3 -C10, or a divalent organic group that combines these .) Represents a functional group. The battery according to any one of (1) to (15), wherein the battery is a repeating unit represented by:
(17) The battery according to any one of (1) to (16), wherein the crosslinked body includes a urethane bond derived from a crosslinking agent,
(18) The crosslinking agent is a polyisocyanate compound having two or more isocyanate groups in the molecule, or an epoxy compound having two or more epoxy groups in the molecule (1) to (17) The battery according to any one of
(19) The number average molecular weight of the copolymer containing the repeating units represented by formula (I) and formula (II) is in the range of 5,000 to 1,000,000 (1) The battery according to any one of to (18),
(20) The electrolyte salt is at least one selected from the group consisting of alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and proton acids (1) to (19) ) The battery according to any one of
(21) The battery according to any one of (1) to (20), wherein the electrolyte salt is a lithium salt.
(22) The block chain C11 is represented by the formula (XXII)

(Wherein R _{10a to} R _12a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R _13a represents an aryl group or a heteroaryl group). Regarding the battery according to any one of (1) to (21), which is a block chain,
(23) The battery according to any one of (1) to (22), wherein the block chain B11, A11, and C11 are arranged in order of B11-A11-C11.
(24) The battery according to any one of (1) to (23), comprising 10 mol or more of a repeating unit represented by the formula (XX),
(25) The battery according to any one of (1) to (24), comprising 5 mol or more of a repeating unit represented by the formula (XXI),
(26) The battery according to any one of (22) to (25), comprising 5 mol or more of a repeating unit represented by the formula (XXII),
(27) The battery according to any one of (1) to (26), wherein m1 in formula (XX) is an integer of 5 to 100,
(28) The battery according to any one of (1) to (26), wherein m1 in formula (XX) is any integer of 10 to 100,
(29) The battery according to any one of (22) to (28), wherein R _13a in formula (XXII) is an aryl group and contains 5 or more repeating units represented by formula (XXII),
(30) Molar ratio ((XX) / ((XXI) + C) of the repeating unit represented by the formula (XX) and the total of the repeating unit represented by the formula (XXI) and the repeating unit contained in the block chain C )) Is in the range of 1/30 to 30/1, the battery according to any one of (1) to (29),
(31) Molar ratio ((XX) / ((XXI)) of the repeating unit represented by the formula (XX), the repeating unit represented by the formula (XXI), and the total of the repeating unit represented by the formula (XXII) + (XXII))) is in the range of 1/30 to 30/1, the battery according to any one of (22) to (30),
(32) Any one of (1) to (31), wherein the number average molecular weight of the copolymer having an order of B11, A11, and C11 is in the range of 5,000 to 1,000,000 The battery according to
(33) The battery according to any one of (1) to (32), wherein the electrode further contains an electrolyte salt,
(34) The battery according to any one of (1) to (33), wherein the electrode contains a copolymer and an electrolyte salt in a range of 0.5 to 15% by weight,
(35) The battery according to any one of (1) to (34), wherein the electrode is a positive electrode and further contains a conductive material.
(36) In a battery comprising a solid polymer electrolyte and an electrode, the solid polymer electrolyte includes a crosslinked polymer having an ion conductive site, and the electrode has a repeating unit having the same repeating unit as that of the copolymer. Regarding batteries characterized by including coalescence,
(37) The battery according to (36), wherein in the copolymer having the same repeating unit as the copolymer, the same repeating unit part is 50 mol% or more.
About.

  The solid polymer electrolyte battery of the present invention has excellent cycle characteristics, is excellent as a secondary battery, and has high industrial utility value.

  The polymer solid electrolyte composition or polymer solid electrolyte used in the battery of the present invention includes a copolymer having a repeating unit represented by formula (I) and formula (II) as an essential constituent unit, and an electrolyte salt. It is characterized by including.

In the repeating unit represented by the general formula (I), R _{1 to} R ₃ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec- A hydrocarbon group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, a t-butyl group, a phenyl group, a naphthyl group, and a benzyl group may be represented, and R ₁ and R ₃ may combine to form a ring. R _4a and R _4b each independently represent a hydrogen atom or a methyl group. R ₅ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-hexyl group, phenyl group, substituted phenyl group, naphthyl group. And a hydrocarbon group such as formyl group, acetyl group, propionyl group, butyryl group and the like, acyl group such as trimethylsilyl group, t-butyldimethylsilyl group, dimethylphenylsilyl group and the like.

R _{1 to} R ₅ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a halogen atom such as a fluorine atom, a chloro atom and a bromine atom, a methyl group, Hydrocarbon groups such as ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, hydrocarbon oxy groups such as nitrile group, nitro group, methoxy group and phenoxy group, Examples thereof include a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.

m represents any integer of 1 to 100, preferably any one of 2 to 50, and the value of m in each repeating unit may be the same or different. When m is 2 or more, R _4a and R _4b may be the same or different. The number of moles of the repeating unit represented by formula (I) is preferably 5 or more, more preferably 10 or more, although it depends on the value of m.

  Specific examples of the repeating unit represented by the formula (I) include repeating units derived from the following compounds. These repeating units may be used alone or in combination of two or more.

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, methoxypolyethylene glycol (the number of units of ethylene glycol is 2 to 100) (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (propylene glycol has 2 to 100 units) (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, phenoxypolypropylene Glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, poly Propylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) Acrylate, “Blenmer PME series” [monomer corresponding to R ₁ = R ₂ = hydrogen atom, R ₃ = methyl group, m = 2 to 90 in formula (I)] (manufactured by NOF Corporation), acetyloxypolyethylene glycol (Meth) acrylate, benzoyloxypolyethylene glycol (meth) acrylate, trimethylsilyloxypolyethylene glycol (meth) acrylate, t-butyldimethylmethyrylio Shi polyethylene glycol (meth) acrylate, methoxy polyethylene glycol cyclohexene-1-carboxylate, methoxy polyethylene glycol - cinnamate.

In the repeating unit represented by the formula (II), R ₆ and R ₈ are each independently a hydrogen atom, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec. -Represents a hydrocarbon group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, a t-butyl group, a phenyl group, a naphthyl group, or a benzyl group, and R ₆ and R ₈ may combine to form a ring. . R ₇ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group or other hydrocarbon oxy group, a carboxyl group, an acid anhydride group, an amino group, an ester group, or Represents an organic group having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group, and R ₉ represents a hydroxyl group, a carboxyl group, an epoxy group, and an acid anhydride. An organic group having at least one functional group selected from the group consisting of a group and an amino group is represented, and specific examples of such an organic group include organic groups represented by the following formulae. However, p1 represents the integer in any one of 1-3 in a following formula.

R _{6 to} R ₉ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a halogen atom such as a fluorine atom, a chloro atom, or a bromine atom. , Hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, carbonization such as nitrile group, nitro group, methoxy group and phenoxy group Examples thereof include a hydrogenoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.

  Among the repeating units represented by the formula (II) exemplified above, the repeating unit represented by the formula (IVA), the formula (V), the formula (VI), or the formula (VII) is particularly preferably exemplified. Can do.

In the formula (IVA), R _{18 to} R ₂₀ are each independently a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, t - butyl group, a phenyl group, a naphthyl group, a hydrocarbon group having 1 to 10 carbon atoms such as benzyl group, R ₁₈ and R ₂₀ may form a ring. R ₂₁ is a C1-C6 alkylene group such as a methylene group, an ethylene group, a 1-methylethylene group or a propylene group, a C6-C10 divalent aromatic hydrocarbon group such as a phenylene group or a naphthylene group, a cyclopropylene group, a cyclopropylene group, A divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms such as a butylene group, a cyclohexylene group, a cyclohexylene group and an adamantanediyl group is represented. R ₂₁ represents a divalent organic group in which two or more selected from the group consisting of the above-described alkylene group, divalent aromatic hydrocarbon group, and divalent alicyclic hydrocarbon group are combined. R _{18 to} R ₂₁ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a halogen atom such as a fluorine atom, a chloro atom, or a bromine atom, and a methyl group. Hydrocarbon groups such as ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, hydrocarbon oxy groups such as nitrile group, nitro group, methoxy group and phenoxy group , Methylthio group, methylsulfinyl group, methylsulfonyl group, amino group, dimethylamino group, anilino group and the like.

  Specific examples of the repeating unit represented by the formula (IVA) include a repeating unit derived from a compound represented by the following formula. These may be used alone or in combination of two or more.

In the formula (V), R _{22 to} R ₂₄ are each independently a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, t -A C1-C10 hydrocarbon group, such as a butyl, a phenyl group, a naphthyl group, a benzyl group, p represents the integer in any one of 1-3, and the substitution position of a hydroxyl group is not specifically limited. Further, R _{22 to} R ₂₄ and an appropriate carbon on the phenyl group may have a substituent, and as such a substituent, specifically, a fluorine atom, a chloro atom, or a bromine Halogen atoms such as atoms, hydrocarbon groups such as methyl, ethyl, n-propyl, phenyl, naphthyl and benzyl, acyl groups such as acetyl and benzoyl, nitrile, nitro, methoxy and phenoxy Examples thereof include a hydrocarbon oxy group such as a group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.

  Specific examples of the repeating unit represented by the formula (V) include a repeating unit derived from a compound represented by the following formula. These can be used alone or in combination of two or more.

In formula (VI), R ₁₈₁ , R ₁₉₁ and R ₂₀₁ are each independently a hydrogen atom, or a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl. Represents a hydrocarbon group having 1 to 10 carbon atoms such as a group, t-butyl group, phenyl group, naphthyl group, and benzyl group, and R ₁₈₁ and R ₂₀₁ may combine to form a ring. R ₂₁₁ are methylene, ethylene, 1-methylethylene group, C1 -C6 alkylene group such as propylene group, a phenylene group, a divalent aromatic hydrocarbon group C6~C10 of such a naphthylene group, a cyclopropylene group, a cycloalkyl Represents a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms such as a butylene group, a cyclohexylene group and an adamantanediyl group. R ₂₁₁ represents a divalent organic group in which two or more selected from the group consisting of the above-described alkylene group, divalent aromatic hydrocarbon group, and divalent alicyclic hydrocarbon group are combined. _R212 represents a hydrogen atom or a C1-C4 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a t-butyl group. R ₁₈₁ , R ₁₉₁ , R _201, and R ₂₁₂ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a fluorine atom, a chloro atom, or a bromine atom. Halogen atom, methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group, benzyl group and other hydrocarbon groups, acetyl group, benzoyl group and other acyl groups, nitrile group, nitro group, methoxy group, phenoxy group Examples thereof include a hydrocarbonoxy group such as methylthio group, methylsulfinyl group, methylsulfonyl group, amino group, dimethylamino group, and anilino group.

  Specific examples of the repeating unit represented by the formula (VI) include a repeating unit derived from a compound represented by the following formula. These can be used individually by 1 type or in mixture of 2 or more types.

In formula (VII), R ₂₈₁ , R ₂₉₁ and R ₃₀₁ are each independently a hydrogen atom, or a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group. Represents a hydrocarbon group having 1 to 10 carbon atoms such as a group, t-butyl group, phenyl group, naphthyl group, and benzyl group, and R ₂₈₁ and R ₃₀₁ may combine to form a ring. R ₃₁₁ represents a hydrogen atom or a functional group represented by the formula (VIII). Wherein (VIII), R ₄₁₁ are methylene, ethylene, 1-methylethylene group, C1 -C6 alkylene group such as propylene group, a phenylene group, a divalent aromatic hydrocarbon group C6~C10 of such naphthylene group Represents a C 3-10 divalent alicyclic hydrocarbon group such as cyclopropylene group, cyclobutylene group, cyclohexylene group, adamantanediyl group. R ₄₁₁ represents a divalent organic group in which two or more selected from the group consisting of the above-described alkylene group, divalent aromatic hydrocarbon group, and divalent alicyclic hydrocarbon group are combined. R ₂₈₁ , R ₂₉₁ , R ₃₀₁ , R ₃₁₁ and R ₄₁₁ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a fluorine atom, a chloro atom, and bromine. Halogen atoms such as atoms, hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, nitrile group, nitro group, methoxy group, Examples thereof include hydrocarbon oxy groups such as phenoxy group, methylthio group, methylsulfinyl group, methylsulfonyl group, amino group, dimethylamino group, and anilino group.

  Specific examples of the repeating unit represented by formula (VII) include a repeating unit derived from a compound represented by the following formula. These can be used individually by 1 type or in mixture of 2 or more types.

  Specific examples of the repeating unit represented by the formula (II) other than the repeating units exemplified by the formula (IVA) to the formula (VII) further include a repeating unit derived from a compound represented by the following formula: be able to. These can be used individually by 1 type or in mixture of 2 or more types.

  The number of moles of the repeating unit represented by the formula (II) is not particularly limited as long as the film having sufficient thermal properties and physical properties can be formed by the crosslinking reaction, but is 5 moles or more. Is preferred.

  In the copolymer having the repeating units represented by the formula (I) and the formula (II), the number of moles of the repeating unit represented by the formula (I) is 5 to 5 with respect to the total number of moles in the copolymer. A range of 99% is preferred. When it is less than 5%, sufficient conductivity cannot be obtained, and when it is more than 99%, sufficient thermal characteristics and physical characteristics may not be obtained.

  The bonding mode of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) is not particularly limited, but is preferably bonded by a block. By bonding with a block, a micro phase separation structure is developed when molding or film formation, and good ionic conductivity is exhibited even in a solid state. The term “bonded by a block” means that the polymer chain containing the repeating unit represented by formula (I) or formula (II) is bonded directly or indirectly with another polymer chain or a linking group. Means. At this time, the other polymer chain may be a homopolymer or a copolymer of two or more. In the case of a copolymer, the bonding state in the polymer chain is not particularly limited, and may be random. It may be a block. Moreover, the polymer chain containing the repeating unit represented by the formula (I) or the formula (II) is a polymer chain consisting only of the repeating unit represented by the formula (I) or the formula (II), the formula (I) or It means a copolymer chain composed of the repeating unit represented by formula (II) and other components.

  In addition to the repeating units represented by formula (I) and formula (II), if necessary, repeating units derived from a polymerizable unsaturated monomer different from formula (I) and formula (II) Can be included.

  The repeating unit derived from the polymerizable unsaturated monomer is not particularly limited as long as it is a repeating unit obtained by polymerizing a monomer that can be polymerized by radical polymerization or ionic polymerization. Or a repeating unit represented by the formula (IV) can be preferably exemplified.

In the formula (III), R _{10 to} R ₁₂ are each independently a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, t - butyl group, a phenyl group, a naphthyl group, a hydrocarbon group having 1 to 10 carbon atoms such as benzyl group, R ₁₃ is a phenyl group, a naphthyl group, an aryl group such as an anthracenyl group, a 2-pyridyl group, 4- Represents a heteroaryl group such as a pyridyl group; R _{10 to} R ₁₃ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a halogen atom such as a fluorine atom, a chloro atom, or a bromine atom, methyl Group, ethyl group, n-propyl group, phenyl group, naphthyl group, benzyl group and other hydrocarbon groups, acetyl group, benzoyl group and other acyl groups, nitrile group, nitro group, methoxy group, phenoxy group and other hydrocarbon oxy groups Examples thereof include a group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.

  Specific examples of the repeating unit represented by the formula (III) include repeating units derived from the following compounds, and these may be used alone or in combination of two or more. Can do.

    Styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, 2,4-dimethylstyrene, m-chlorostyrene, p-chlorostyrene, 1-vinylnaphthalene, 9-vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, methyl cinnamate and the like.

In the formula (IV), R _{14 to} R ₁₆ are each independently a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, t -Represents a C1-C10 hydrocarbon group such as a butyl group, a phenyl group, a naphthyl group, or a benzyl group, R ₁₄ and R ₁₆ may combine to form a ring, and R ₁₇ represents a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, phenyl group, naphthyl group, benzyl group, cyclopropyl group, cyclohexyl group, norbornyl group, adamantyl Represents a heterocyclic group such as a C1-C12 hydrocarbon group, 2-pyridyl group, 4-pyridyl group, etc., particularly a C1-C12 alkyl group, an aryl group, an alicyclic hydrocarbon group, a heterocyclic ring Like group It can be laid exemplified.

R _{14 to} R ₁₇ may have a substituent on an appropriate carbon atom. Specific examples of such a substituent include a halogen atom such as a fluorine atom, a chloro atom, or a bromine atom, and a methyl group. Hydrocarbon groups such as ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, hydrocarbon oxy groups such as nitrile group, nitro group, methoxy group and phenoxy group , Methylthio group, methylsulfinyl group, methylsulfonyl group, amino group, dimethylamino group, anilino group and the like.

  Specific examples of the repeating unit represented by the formula (IV) include repeating units derived from the following compounds. These may be used alone or in combination of two or more. Can do.

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic Isobornyl acid, dicyclopentenyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 1-methyleneadamantyl (meth) acrylate, (meth) acrylic acid 1 -Ethylene adamantyl, 3,7-dimethyl-1-adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, norbornane (meth) acrylate, menthyl (meth) acrylate, n- (meth) acrylate Propyl, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isomethyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, (meth) 3-oxocyclohexyl acrylate, butyrolactone (meth) acrylate, mevalonic lactone (meth) acrylate.

  A repeating unit different from the repeating units represented by formula (I) and formula (II), and a repeating unit other than the repeating units represented by formula (III) and formula (IV), The repeating unit induced | guided | derived can be illustrated, These can be used individually by 1 type or in mixture of 2 or more types.

  1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,6-hexadiene, 4, Conjugated dienes such as 5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, α, β-unsaturated carboxylic imides such as N-methylmaleimide, N-phenylmaleimide, ( Α, β-unsaturated nitriles such as (meth) acrylonitrile.

  The number of moles of the repeating unit derived from the polymerizable unsaturated monomer other than the repeating unit represented by formula (I) and formula (II) is not particularly limited, but the repeating unit represented by formula (I) Is preferably 5 mol or more, and more preferably 10 mol or more.

  Further, the total number of moles of repeating units derived from a polymerizable unsaturated monomer other than the repeating units represented by the formula (I) and the repeating units represented by the formulas (I) and (II) is: It is preferably in the range of 1 to 95% based on the total number of moles of repeating units in the copolymer. If it is 1% or less, the ionic conductivity is lowered, and if it is 95% or more, the thermal characteristics and physical characteristics may be lowered.

  In the present invention, a polymer chain (A) containing a repeating unit represented by formula (I), a polymer chain (B) containing a repeating unit represented by formula (II), a formula (I) and a formula (II) The bonding state of the polymer chain (C) containing a repeating unit derived from an unsaturated bond monomer other than the repeating unit is not particularly limited, and is preferably bonded by a block. By bonding with a block, a micro phase separation structure is developed when molding or film formation, and good ionic conductivity is exhibited even in a solid state. The term “bonded by a block” means that each polymer chain (A), (B), (C) is bonded directly or indirectly by another polymer chain or a linking group. Further, a taper block in which the component ratio between repeating units constituting each polymer chain gradually changes is also included in the block bond referred to in the present invention. In this case, the other polymer chain may be a homopolymer or a copolymer of two or more. In the case of a copolymer, the bonding state in the polymer is not particularly limited, and is random, tapered block, It may be a block. Further, the polymer chain (A) or the like containing a repeating unit represented by the formula (I) or the like is represented by a polymer chain consisting only of a repeating unit represented by the formula (I) or the like, or a formula (I) or the like. It means a copolymer chain composed of repeating units and other components.

  As the block bonding state of each polymer chain (A), (B), (C), [(A)-(B)] j, [(A)-(B)-(C)] j, [(A) -(B)-(A)] j, [(C)-(B)-(A)-(B)-(C)] j (j represents an integer of 1 or more), etc. it can.

  Moreover, each said block polymer can also be made into the block copolymer by which the segment was extended or branched as represented by following formula (11)-(14) through the residue of a coupling agent, respectively. In the formula, w represents an integer of 1 or more, and X represents a residue of the coupling agent.

  Especially, when it is a non-polar polymer chain and a polymer chain (C) is contained, a microphase separation state can be expressed and ion conductivity can be improved.

  When a polymer chain having a repeating unit represented by the formula (III) is used as the polymer chain (C), the copolymer in the present invention is a block chain A having a repeating unit represented by the formula (I), In the copolymer, block chains B1 and B2 having a repeating unit represented by the formula (II) and block chains C1 and C2 having a repeating unit represented by the formula (III) are B1, C1, A, A copolymer disposed in the order of C2 and B2 can be preferably used. Each block chain is arranged in the order of B1, C1, A, C2, and B2. Even if each block chain is directly bonded, it sandwiches other structural units such as a linking group and a polymer chain. Means that they may be bonded together. In addition to the repeating unit formulas (I) to (III) to which the respective block chains correspond, the other repeating units may include other repeating units included as a constituent unit. The polymerization mode with the repeating unit formulas (I) to (III) is not particularly limited, and may be any polymerization mode such as random polymerization, block polymerization, or alternating polymerization. Further, when it contains other polymer chains as other repeating units as a structural unit, it may be a homopolymer or a copolymer of two or more, and in the case of a copolymer, the bonding state in that is particularly The gradient is not limited and may be random, block, or a gradient in which the component ratio gradually changes. Especially, the case where each block chain | strand is couple | bonded and arranged in order of B1-C1-A-C2-B2 is preferable. In this case, “bonded” means that each block chain is directly bonded, or is bonded via a low-molecular linking group such as an oxygen atom or an alkylene group. Also, B1 and B2, C1 and C2 that are arranged or bonded may be the same or different.

  In this case, the number of moles of the repeating unit represented by the formula (I) in the copolymer having the repeating unit represented by the formula (I), the formula (II) and the formula (III) is 9.9 to 80%. The number of moles of the repeating unit represented by the formula (II) is in the range of 0.1 to 50%, and the number of moles of the repeating unit represented by the formula (III) is 19.9 to 90%. It is preferable that it is the range of these. When the repeating unit represented by the formula (I) is 9.9% or more, more sufficient conductivity can be obtained, and within 80%, more sufficient thermal characteristics and physical characteristics can be obtained. When the repeating unit represented by the formula (II) is 0.1% or more, the crosslinking density is not low, and sufficient thermal and physical properties can be obtained. Sex can be obtained. When the repeating unit represented by the formula (III) is 19.9% or more, more sufficient thermal characteristics and physical characteristics can be obtained, and within 90%, more sufficient conductivity can be obtained. .

  The number average molecular weight of the copolymer of the present invention comprising repeating units represented by formulas (I) and (II), and other repeating units such as formula (III) and formula (IV) added as necessary Although there is no particular limitation, 5,000 to 1,000,000 can be preferably exemplified. When it is larger than 5,000, the thermal characteristics and physical characteristics are improved, and when it is smaller than 1,000,000, the moldability or film formability is improved. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, but in order to form a microphase separation structure described later, 1.01 to 2.50, A range of 1.01-1.50 is preferred.

  The copolymer used in the present invention is a compound represented by the following formula (XI) or formula (XII), using a known method such as a radical polymerization method, a living radical polymerization method, or a living anion polymerization method. Can be manufactured.

  Further, for repeating units derived from unsaturated monomers other than the repeating units represented by formula (I) and formula (II) incorporated as necessary, for example, the following formula (XIII), formula (XIV) It can manufacture similarly by further using the monomer represented by.

R _{1 to} R ₁₇ in the formulas (XI) to (XIV) have the same meaning as described above.

Further, taking a block copolymer which is a preferable polymerization form as an example, it will be described in more detail.
(A) A method of producing a block copolymer by synthesizing one of the repeating units represented by formula (I) or formula (II) and then synthesizing the other.
(B) a method of separately synthesizing repeating units represented by formula (I) and formula (II), and then coupling each of them by a coupling reaction to produce a block copolymer;
(C) A method for producing a block copolymer by synthesizing a repeating unit represented by the formula (II) using a polymerization initiator having a repeating unit represented by the formula (I) in the molecule;
(D) a method for producing a block copolymer by synthesizing a repeating unit represented by formula (I) using a polymerization initiator having a repeating unit represented by formula (II) in the molecule;
Etc. can be further exemplified.

  In particular, in the case of producing a copolymer arranged in the order of B1, C1, A, C2, and B2, the compounds represented by formula (XI), formula (XII), and formula (XIII) A known method such as a living radical polymerization method using a transition metal complex as a catalyst and an organic halogen compound containing one or more halogen atoms as a polymerization initiator, a living radical polymerization method using a stable radical, or a living anion polymerization method. In particular, a living radical polymerization method using a transition metal complex as a catalyst and an organic halogen compound containing one or more halogen atoms as a polymerization initiator can be particularly preferably exemplified.

  More specifically, (B) each block chain such as a bifunctional block chain obtained by reacting the compound represented by formula (XI) with a bifunctional initiator in a living radical polymerization method is included. A method in which a macroinitiator is further reacted with a monomer that constitutes another block chain and then the block chain is extended, or (b) expressed by formula (XII) instead of formula (XI) Using the compound to be prepared, using a monofunctional initiator, the others are performed in the same manner as in (a), and the method of producing by sequentially extending the block chain from the end, or (c) each block chain, or each block chain Examples thereof include a method in which a part is polymerized in a predetermined sequence and then produced by a coupling reaction. The living radical polymerization can be performed using a transition metal complex as a catalyst and an organic halogen compound having one or more halogen atoms in the molecule as an initiator.

As a method for producing a copolymer by the living radical polymerization method, specifically,
(I) For example, after the conversion rate of the first monomer reaches 100%, the second monomer is added to complete the polymerization, and this is repeated to obtain a block copolymer A method of sequentially adding the body,
(Ii) Even if the conversion rate of the first monomer does not reach 100%, the polymerization is continued by adding the second monomer at the stage where the target degree of polymerization or molecular weight is reached, and random parts are formed between the block chains. A method for obtaining a gradient copolymer in which
(Iii) Even if the conversion rate of the first monomer does not reach 100%, the reaction is stopped once it reaches the target degree of polymerization or molecular weight, and the polymer is taken out of the system. A method of obtaining a block copolymer by intermittently advancing copolymerization by adding other monomers as an initiator,
Etc. can be illustrated.

  The reaction conditions used in each polymerization method are not particularly limited, and known reaction conditions can be used.

  When living radical polymerization method and living anion polymerization method are used and a compound having an active hydrogen such as a hydroxyl group or a carboxyl group is used in the molecule, known protection such as silylation, acetalization, BOC conversion, etc. It can be produced by protecting the active hydrogen by the reaction and then subjecting it to a polymerization reaction, followed by a deprotection reaction with an acid, alkali or the like after the polymerization.

  Tracking of the copolymerization reaction process and confirmation of the completion of the reaction can be easily performed by gas chromatography, liquid chromatography, gel permeation chromatography, membrane osmotic pressure method, NMR or the like. After completion of the copolymerization reaction, a copolymer can be obtained by applying a normal separation / purification method such as column purification, or filtering and drying a polymer component deposited in, for example, water or a poor solvent. it can.

  Examples of the polymer of the present invention include a polymer segment (P1) having ionic conductivity, a polymer segment (P2) having no ionic conductivity, and a polymer segment (P3) having a crosslinking point, such as P3, P2, P1, P2, Examples of the polymer segment (P1) having an ionic conductivity are the block chain A, and the polymer chain (P2) having no ionic conductivity is the block chain. B1 and B2 can be specifically exemplified as the polymer chain (P3) having a crosslinking point, and the block chain C1 and C2 can be specifically exemplified. As a method for producing the polymer of the present invention, the method for producing the copolymer is as follows. Specific examples can be given.

  The composition for a polymer solid electrolyte of the present invention is characterized by containing the above-mentioned copolymer and an electrolytic salt, and further preferably contains a crosslinking agent. The copolymer may be a mixture of two or more types having different structural units, but is preferably a copolymer having a microphase separation structure.

  The crosslinking agent is not particularly limited as long as it crosslinks by reacting with a reactive site such as a hydroxyl group contained in the repeating unit represented by the formula (II). Specifically, tolylene diisocyanate ( TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), triphenylmethane triisocyanate, polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHMDI), tetramethylxylylene diisocyanate (m-TMXDI) Polyisocyanates such as isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), 1,5-naphthalene diisocyanate, etc., or trimer compounds of these polyisocyanates, these polyisocyanates A reaction product of an isocyanate and a polyol can be exemplified. Moreover, you may use the blocked isocyanate which blocked some or all of the isocyanate group using well-known blocking agents, such as a phenol compound and oximes. Moreover, chain extenders, such as ethylene glycol, propylene glycol, hexamethylene-1,6-diol, polyethylene glycol, can also be used together as needed.

  When a polyisocyanate compound is used, if necessary, heavy metal compounds such as amines such as triethylamine, triethylenediamine and hexamethylenetetramine, cobalt naphthenate, tetra-n-butyltin and dibutyltin dilaurate are used as curing accelerators. Etc. can also be used.

  Other crosslinking agents include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, polyglycol type epoxy. Examples include compounds containing two or more epoxy groups such as resins, alicyclic epoxy resins, glycidylamine type epoxy resins, isocyanuric acid type epoxy resins, halogenated bisphenol A type epoxy resins, and the like. As a curing accelerator, tertiary amines such as benzyldimethylamine and imidazoles such as 2-ethylimidazole can be used.

  Furthermore, as other crosslinking agents, those usually used as curing agents for epoxy resins, for example, aliphatic polyamines such as triethylenediamine and triethylenetetramine, aromatic polyamines such as diaminodiphenylmethane, N-aminoethyl Alicyclic polyamines such as piperazine, acid anhydrides such as 4-methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, phenol novolac resin, cresol novolac resin, poly-p-hydroxystyrene, etc. Polyphenols, dicyandiamide, polyamide resin, and the like. Other examples of the curing agent include boron trifluoride amine complex, various onium salts, and the like. Further, when acid anhydrides or polyphenols are used as a crosslinking agent, known curing accelerators such as the above-mentioned tertiary amines and imidazoles can be used as necessary.

  Particularly preferred examples of the crosslinking agent include polyisocyanate compounds or polyepoxy compounds, and these crosslinking agents can be used alone or in combination of two or more. Moreover, these hardening | curing agents or hardening accelerators can also be used individually by 1 type and in combination of 2 or more types. Moreover, when it has an epoxy group in the repeating unit represented by Formula (II), an epoxy hardening | curing agent shall become a crosslinking agent apparently.

  The combination of the reactive group and the crosslinking agent contained in the repeating unit represented by the formula (II) is not particularly limited as long as it reacts. Specifically, the combination is represented by the formula (II). When the reactive group in the repeating unit is a hydroxyl group, a polyisocyanate compound is preferable as the crosslinking agent, and when the reactive group is a carboxyl group, an amino group, or a phenolic hydroxyl group, a polyepoxy compound is preferable as the crosslinking agent.

  The amount of the crosslinking agent to be used is not particularly limited, but is preferably in the range of 0.01 to 2 mol, more preferably 0.1 to 1 mol, per 1 mol of the repeating unit represented by the formula (II) having a crosslinking point. A range is preferred. If it is 0.01 mol or more, more sufficient thermal characteristics and physical characteristics can be obtained, and if it is within 2, more sufficient conductivity can be obtained.

The electrolyte salt used in the present invention is not particularly limited, and an electrolyte containing an ion that is desired to be a carrier by charge may be used, but the dissociation constant in the polymer solid electrolyte obtained by curing is large. Desirably, an alkali metal salt, a quaternary ammonium salt such as (CH ₃ ) ₄ NBF ₆ , a quaternary phosphonium salt such as (CH ₃ ) ₄ PBF ₆ , a transition metal salt such as AgClO _4, hydrochloric acid, perchloric acid, Protic acids such as borohydrofluoric acid can be used, and alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts or transition metal salts are preferably used.

Specific examples of the alkali metal salt that can be used include LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC (CH ₃ ) (CF ₃ SO ₂ ) ₂ , LiCH (CF ₃ SO ₂ ) ₂ , LiCH ₂ (CF ₃ SO ₂ ), LiC ₂ F ₅ SO ₃ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiB (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ , KI, LiCF ₃ CO ₃ , NaClO ₃ , NaSCN, KBF ₄ Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) _{2 and the} like can be exemplified, and these electrolyte salts may be mixed and used, among which lithium salt is preferable.

  The amount of the electrolyte salt added is in the range of 0.005 to 80 mol%, preferably 0.01 to 50 mol%, based on the alkylene oxide unit of the copolymer that is the base polymer of the polymer electrolyte. . The composition for a solid polymer electrolyte of the present invention can be produced by adding and mixing (combining) an electrolyte salt with the above-described copolymer and cross-linking agent. , A method in which a copolymer, a crosslinking agent and an electrolyte salt are dissolved in an appropriate solvent such as tetrahydrofuran, methyl ethyl ketone, acetonitrile, ethanol, dimethylformamide, and a copolymer, a crosslinking agent and an electrolyte salt are mechanically heated at room temperature or under heating. And the like.

  As the polymer solid electrolyte composition of the present invention, polymer segment (P1) having ionic conductivity, polymer segment (P2) having no ionic conductivity, and polymer segment (P3) having a crosslinking point are represented by P3, P2 , P1, P2, and P3 are not particularly limited as long as they include a polymer having a sequence arrangement of P1, P2, and P3, a cross-linking agent, and an electrolyte salt. Examples of the polymer segment (P2) having no property include the block chains B1 and B2, and examples of the polymer segment (P3) having a crosslinking point include the block chains C1 and C2. Specific examples of the agent and the electrolyte salt are the same as those described above.

  The polymer solid electrolyte of the present invention is not particularly limited as long as it contains a crosslinked polymer and an electrolyte salt obtained by the reaction of the above-mentioned copolymer and an electrolyte salt, preferably a copolymer and a crosslinking agent. Those having a network type microphase separation structure are preferred. Moreover, as a crosslinked polymer, it was cured using a crosslinking agent in a range of 0.01 to 2 mol, particularly in a range of 0.1 to 1 mol, with respect to 1 mol of the repeating unit represented by the formula (II). Including a polyisocyanate compound having two or more isocyanate groups in the molecule, an epoxy compound having two or more epoxy groups in the molecule as a crosslinking agent, and a urethane bond derived from the crosslinking agent Those having a microphase separation structure are preferable. Such a crosslinked polymer can be produced by subjecting a copolymer and a crosslinking agent to a crosslinking reaction with various energies such as heat, ultraviolet rays, infrared rays, far infrared rays, and microwaves.

  As a method for producing a solid polymer electrolyte of the present invention, (i) a copolymer and a cross-linking agent are controlled before they are completely cross-linked using various energies such as heat, and further, an electrolyte salt is added to cross-link, Solidification method (ii) Two or more kinds of copolymers having different crosslinking conditions and one or more kinds of crosslinking agents are crosslinked under the condition that only one copolymer is crosslinked, and then an electrolyte salt is added. And (iii) two or more kinds of copolymers having different crosslinking conditions, one or more kinds of crosslinking agents, and an electrolyte salt under the condition that only one copolymer is crosslinked. Examples of the method of crosslinking and solidification after crosslinking are further exemplified.

  In particular, the resin composition for a solid polymer electrolyte is formed into a sheet shape, a film shape, a film shape, and the like, and then crosslinked by the energy to function as an ion conductive sheet / membrane / film. -It is preferable to use a film-like cross-linked polymer. In this case, the degree of freedom of the processed surface is widened, which is a great advantage in application.

  As a means for producing a polymer solid electrolyte such as a sheet, the resin composition for a polymer solid electrolyte is formed on a support by various coating means such as a roll coater method, a curtain coater method, a spin coat method, a dip method, and a cast method. Then, a cross-linking reaction is performed with the energy, and then the support is removed to obtain a solid polymer electrolyte such as a sheet.

  The polymer solid electrolyte of the present invention includes a polymer segment (P1) having ionic conductivity, a polymer segment (P2) not having ionic conductivity, and a polymer segment (P3) having a crosslinking point, such as P3, P2, P1, The polymer segment (P1) having ion conductivity is not particularly limited as long as it contains a crosslinked polymer obtained by the reaction of a polymer having an arrangement of P2 and P3 with a crosslinking agent, and an electrolyte salt. Is specifically the block chain A, the polymer chain (P2) having no ion conductivity is the block chain B1 or B2, and the polymer segment (P3) having a crosslinking point is the block chain C1 or C2. Examples of the crosslinking agent and the electrolyte salt include those described above. Moreover, as a polymer which has arrangement | positioning of the order of said P3, P2, P1, P2, P3, what has a micro phase-separation structure is preferable.

  The ion conductive membrane of the present invention is a membrane comprising a polymer segment having ion conductivity (P1), a polymer segment having no ion conductivity (P2), and a polymer having a crosslinked polymer segment (P4), The membrane includes a membrane including a natework type microphase separation structure, a polymer segment (P1) having ionic conductivity, a polymer segment (P2) having no ionic conductivity, and a polymer segment (P3) having a crosslinking point. A membrane containing a crosslinked polymer obtained by the reaction between a polymer and a crosslinking agent, and is not particularly limited as long as the membrane contains a natework type microphase separation structure in the membrane, but has the above P1, P2, and P3 It is preferable that the polymer forms a microphase separation structure. As the polymer segment (P1) having ion conductivity, the block chain A is used. As the polymer segment (P2) having no ion conductivity, the block chain B1 or B2 is used as the polymer segment (P3) having a crosslinking point. Can specifically illustrate the block chains C1 and C2, and the crosslinking agent can be specifically exemplified as the crosslinked polymer segment (P4). The ion conductive membrane of the present invention has a structure including a network-type microphase separation structure in the membrane, thereby maintaining ionic conductivity (conductivity), physical properties, thermal properties, particularly membrane strength. Can be improved.

  The polymer solid electrolyte battery of the present invention includes a solid electrolyte formed by using the above-described polymer solid electrolyte or the polymer solid composition, and an electrode.

  The polymer solid electrolyte battery is, for example, a method in which a polymer solid electrolyte is used as a molded body such as a film in advance and incorporated between electrodes, or a composition containing a polymer such as a copolymer described above on the electrode and an electrolyte salt. The polymer solid electrolyte is formed on the positive electrode by various coating means such as a roll coater method, a curtain coater method, a spin coat method, a dip method, a cast method, and the other electrode is disposed. Can be manufactured.

  As an electrode used for a battery, an electrode active material, a copolymer described above, or a block chain A11 having a repeating unit represented by the formula (XX) and a block chain having a repeating unit represented by the formula (XXI) It is preferable that B11 and the block chain C11 contain a copolymer having an order of B11, A11, and C11, and an electrolyte salt can be added as necessary. Further, when the electrode is a positive electrode, it is preferable that the electrode further contains a conductive material.

  The block chain C11 represents a block chain having an arbitrary component, and the block chain B and the block chain C11 may be the same or different. In particular, a block chain having a repeating unit represented by the formula (XXII) can be preferably exemplified.

  Having a repeating unit represented by the formula (XX) or (XXI) in the block chain A11 or B11 means that each block chain includes other repeating units as a constituent unit in addition to the corresponding repeating unit. Means both. Further, when other repeating units are included as constituent units, the polymerization mode with the repeated units represented by the respective formulas is not particularly limited, and any polymerization mode such as random polymerization, block polymerization, alternating polymerization, etc. may be used. I do not care.

  Each block chain has an order of B11, A11, and C11. Even if each block chain is directly bonded, it is sandwiched between other structural units such as a linking group and a polymer chain. Means that they may be bonded together. When other polymer chains are included as a structural unit, it may be a homopolymer or a copolymer of two or more, and in the case of a copolymer, the bonding state is not particularly limited, and may be random, block Or a gradient in which the component ratio gradually changes. Especially, the case where each block chain | strand has the arrangement | sequence couple | bonded by B11-A11-C11 is preferable. In this case, “bonded” means that each block chain is directly bonded, for example, bonded via a low-molecular linking group such as an oxygen atom or an alkylene group.

  The repeating unit represented by the formula (XX) corresponds to the repeating unit represented by the formula (I), and each symbol included in the formula excludes a part of the meaning represented by m1, The same meaning as each symbol of the same position contained in Formula (I) is represented, and the same specific example can be illustrated. M1 is particularly preferably an integer of 5 to 100, and more preferably an integer of 10 to 100.

The repeating unit represented by the formula (XXI) corresponds to the repeating unit represented by the formula (III), and each symbol contained in the formula excludes a part of the meaning represented by R _9a. The same meaning as each symbol of the same position contained in Formula (III) is represented, and the same specific example can be illustrated.

The repeating unit represented by the formula (XXII) corresponds to the repeating unit represented by the formula (III), and each symbol included in the formula includes each symbol at the same position included in the formula (III). It represents the same meaning and can illustrate the same specific example. In particular, the case where R _13a is an aryl group and contained in an amount of 5 mol or more can be preferably exemplified.

  The amount of each repeating unit contained in the copolymer is not particularly limited, but the repeating unit represented by the formula (XX) is preferably 10 mol or more, and the formula (XXI) and the formula (XXII) It is preferable that the repeating unit represented by) is 5 mol or more.

  The copolymer can contain a repeating unit different from the repeating units represented by the formulas (XX) to (XXII) as a constituent unit, and examples of the repeating unit derived from the following compound as such a repeating unit. can do. Moreover, these repeating units can be used as a repeating unit in the block chain C11 when the repeating unit represented by the formula (XXII) is not included. These repeating units may be used alone or in combination of two or more.

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic Isobornyl acid, dicyclopentenyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 1-methyleneadamantyl (meth) acrylate, (meth) acrylic acid 1 -Ethylene adamantyl, 3,7-dimethyl-1-adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, norbornane (meth) acrylate, menthyl (meth) acrylate, n- (meth) acrylate Propyl, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isomethyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, (meth) (Meth) acrylic acid such as 3-oxocyclohexyl acrylate, butyrolactone (meth) acrylate, mevalonic lactone (meth) acrylate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,6-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene , Conjugated dienes such as chloroprene, N-methylmaleimide, N-phenylmale alpha, such as de, beta-unsaturated carboxylic acid imides, (meth) alpha, such as acrylonitrile, beta-unsaturated nitriles and the like.

  Furthermore, it has a double bond capable of copolymerization with a monomer that generates a repeating unit represented by formulas (XX) to (XXII) in the molecule, and further has a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride. A repeating unit having in the molecule thereof at least one functional group selected from the group consisting of a group and an amino group can be included as a structural unit, and as such a repeating unit, a repeating unit derived from the following compound: Units can be exemplified. These repeating units may be used alone or in combination of two or more.

  The molar ratio ((XX) / ((XXI) + C11)) of the repeating unit represented by the formula (XX), the repeating unit represented by the formula (XXI) and the repeating unit contained in the block chain C is: The range of 1/30 to 30/1 is preferable. When the block chain C11 contains a repeating unit represented by the formula (XXII), the repeating unit represented by the formula (XXII) should be applied instead of the repeating unit contained in the block chain C11 in the above mixing ratio. Can do.

  The number average molecular weight of the copolymer of the present invention is not particularly limited, but is preferably in the range of 5,000 to 1,000,000. When the number average molecular weight is smaller than 5,000, the thermal characteristics and physical characteristics are deteriorated, and when it is larger than 1,000,000, the moldability or film formability is deteriorated. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, but in order to form a microphase separation structure described later, 1.01 to 2.50, A range of 1.01-1.50 is preferred.

  The copolymer is not particularly limited as long as it has block chains A11, B11, and C11 in a specific arrangement. However, in order to maintain high ionic conductivity, a microphase separation structure is used in the membrane structure. In particular, it is preferable to adopt a configuration that expresses a network-type microphase separation structure.

  The above copolymer is a living radical polymerization method using a compound having a polymerizable double bond for deriving each repeating unit, using a transition metal complex as a catalyst and an organic halogen compound containing one or more halogen atoms as a polymerization initiator. , Can be produced using known methods and conditions such as living radical polymerization method and living anion polymerization method using stable radicals. Among them, a transition metal complex is used as a catalyst, and an organic halogen compound containing one or more halogen atoms is initiated. A living radical polymerization method using an agent can be preferably exemplified.

The electrode active material to be used is not particularly limited, and various materials conventionally known as electrode active materials can be used. Specifically, various carbon-based materials obtained by simple metals such as metallic lithium, metallic silver, metallic zinc, alloys such as Li-Al, graphite, carbon black, fluorinated graphite, polyacetylene, firing, thermal decomposition, CVD, etc. , MnO ₂ , CoO ₂ , V ₂ O ₅ , V ₂ O ₆ , TiO ₂ , WO ₂ , Cr ₂ O ₅ , Cr ₃ O ₈ , CuO, Cu ₂ V ₂ O ₇ , Bi ₂ O ₃ , Bi ₂ PB Metal oxides such as ₂ O ₅ , Mo ₈ O ₂ , LiCoO ₂ , chalcogenides such as TiS ₂ , TiS ₃ , MoS ₂ , CuCo ₂ S ₄ , VSe ₂ , NbSe ₂ CrS ₂ , NbSe ₃ , Ag ₂ CrO ₄ Examples thereof include silver oxyacids such as Ag ₂ MoO ₄ , AgIO ₃ and Ag ₂ P ₂ O ₇ , and π-conjugated polymers such as polyaniline, polypyrrole, polythiophene and poly-p-phenylene.

The electrolyte salt to be used can be exemplified by the same electrolyte salt used for the polymer electrolyte salt, and in particular, LiClO ₄ , LiCF ₃ SO ₃ , LiBF ₄ , LiPF ₄ , LiAsF ₆ , LiAlCl ₄ , LiBr, LiSCN , LiI, LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ SO ₂ ) ₂ , NaClO ₄ , NaI, NaBF ₄ , NaSCN, KPF ₆ , KSCN, and other alkali halides, and alkalis having organic acid anions Metal salts can be preferably exemplified, and among them, lithium salts can be more preferably exemplified.

  Although it does not specifically limit as a conductive material to be used, Specifically, ketjen black, carbon black, acetylene black, graphite, coke powder, graphite and the like can be exemplified, and among them, ketjen black, acetylene black, etc. It can be illustrated preferably.

  The amount of the polymer such as a copolymer and the electrolyte salt contained in the electrode is not particularly limited, but is preferably in the range of 0.5 to 15% by weight of the entire electrode composition (excluding the support). If it is less than 0.5 weight, the contact resistance with the electrolyte is large, and if it is 15 weight% or more, the conductivity is lowered.

  The method for producing the electrode is not particularly limited. For example, a method of casting or coating a solution containing a polymer and an electrolyte salt on a layer containing an electrode active material prepared on a support, an electrode active material, a polymer, and Examples thereof include a method of casting or coating a solution containing an electrolyte salt on a support.

  The polymer to be used is preferably a polymer that exhibits conductivity when combined with an electrolyte salt, and more preferably a polymer that is used as an electrolyte.

  The electrolyte salt used is preferably a salt used as an electrolyte, and the salt used as an electrolyte and the salt used in the electrode may be the same or different in the same element, but are the same. preferable. Specifically, the same electrolyte salt as described above can be exemplified.

  The solid content concentration of the solution containing the polymer and the electrolyte salt is not particularly limited, but specifically, a range of 0.5 to 10% by weight can be preferably exemplified.

  The layer containing an electrode active material preferably contains at least one selected from polymers used for binders and electrolytes in addition to the electrode active material. The binder is not particularly limited as long as it is a compound that fixes an electrode active material on a support and does not affect conductivity. Specifically, fluorine such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, etc. Resins and rubbers such as styrene butadiene rubber can be exemplified, and among them, a fluororesin (particularly PVDF) can be particularly preferably exemplified.

  The polymer used as the electrolyte is not particularly limited as long as it is a polymer that exhibits conductivity when combined with an electrolyte salt. The polymer used as the battery electrolyte and the polymer used as the electrode may be the same or in the same element. They may be different but are preferably the same.

  The layer containing an electrode active material can be produced, for example, by applying a solution containing at least one selected from an electrode active material and a polymer used as a binder and an electrolyte on a support and drying. The coating method is not particularly limited, and methods such as a roll coater method, a curtain coater method, a spin coat method, a dip method, and a cast method can be used.

  The number of times of casting or coating is related to the solid content concentration of the solution to be used, but it is preferable to carry out multiple times. The method for coating is not particularly limited, but a method in which the solvent remains after coating so that the polymer and the electrolyte salt penetrate into the layer containing the electrode active material is preferable. After casting or coating the solution, the solvent is preferably distilled off gradually under normal pressure or reduced pressure.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to an Example.

(1) Synthesis of B-A-B type block graft copolymer Under argon atmosphere, 2.9 g (3 mmol) of dichlorotris (triphenylphosphine) ruthenium, 1 mol of toluene, methoxypolyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd.) Manufactured by Bremermer PME-1000) and mixed uniformly, and then 1.6 g (12 mmol) of di-n-butylamine and 1.1 g (6 mmol) of 2,2-dichloroacetophenone were added and stirred. The polymerization reaction was started by heating to 0 ° C. After 41 hours from the start of the polymerization reaction, the polymerization reaction was stopped by cooling the polymerization reaction system to 0 ° C. The polymerization rate was 52.0%. Subsequently, column purification of the polymerization solution was performed to remove metal complexes, unreacted monomers, and the like, and then toluene was distilled off under reduced pressure to obtain poly-methoxypolyethylene glycol monomethacrylate (abbreviated as P-PME1000-19). The obtained P-PME1000-19 was a polymer having a number average molecular weight (Mn) of 23800.

  Under an argon atmosphere, 375 g of toluene, 0.5 g (0.63 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, 100 g (0.42 mmol) of P-PME1000-19: 25 g (240 mmol) of styrene , And then uniformly mixed, 0.32 g (2.5 mmol) of di-n-butylamine was added, and the mixture was heated to 100 ° C. with stirring to initiate the polymerization reaction. After 94 hours from the start of the polymerization reaction, the polymerization reaction system was cooled to 0 ° C. to stop the polymerization reaction. The polymerization rate of styrene was 43%. After column purification of the polymerization solution to remove the metal complex and unreacted monomer, toluene was distilled off under reduced pressure, and GPC analysis was performed on the resulting copolymer. As a result, a monodisperse polymer with Mn = 264000 was obtained. Yes, when 13CNMR was measured, it was found that the ratio of moles of PME-1000 repeating units to the total number of moles of repeating units in the copolymer was 90%, and the ratio of moles of St repeating units was 10%. PME-1000-b-St).

(2) Preparation of electrode 340 mg of LiCoO ₂ powder (manufactured by Nippon Chemical Industry Co., Ltd., cell seed C-10, particle size: 10 to 15 μm) and 40 mg of ketjen black (KB: manufactured by ketjen black international) were weighed and mixed well in a mortar. To this was added 170 mg of a 12 wt% N-methylpyrrolidone (NMP) solution of polyvinylidene fluoride (PVdF: Aldrich, molecular weight 534,000), and mixed well with a spatula, and the mixture was placed on an aluminum foil current collector having a thickness of 80 mm × 200 mm × 50 μm. The positive electrode layer was formed by applying with a doctor blade having a width of 40 mm and a gap of 50 μm, followed by vacuum drying at 100 ° C. for 24 hours, and pressing at ²⁰ Mpa / cm ² . The positive electrode thickness was 32 μm, and the content of LiCoO _{2 was} 5 mg / cm ² .

200 mg of the B-A-B type block graft polymer prepared above was dissolved in tetrahydrofuran (THF: Wako Pure Chemicals special grade reagent) to give a 20% strength by weight solution. To this solution, 0.02 g of anhydrous LiClO ₄ (Wako Pure Chemicals special grade reagent) was dissolved, and acetonitrile (AN: Wako Pure Chemicals special grade reagent) was added to prepare a solution containing a polymer and an electrolyte salt at a concentration of 5% by weight. 2 g of this solution was cast on a positive electrode sheet having a coating area of 50 mm × 50 mm prepared in advance, and after removing the solvent at room temperature under normal pressure under a nitrogen stream, heated at 60 ° C. under normal pressure for 1 hour under a nitrogen stream, The mixture was heated for 1 hour at 80 ° C. under normal pressure in a nitrogen stream. Then, it was dried under vacuum at 80 ° C. for 1 hour, and dried under vacuum at 120 ° C. for 3 hours to obtain a polymer-containing positive electrode.

(3) Synthesis of C—B—A—B—C type block / graft copolymer Under an argon atmosphere, 0.96 g of dichlorotris (triphenylphosphine) ruthenium was added to 300 g of toluene that had been previously degassed with argon. 1 mmol), PME-1000: 100 g (90 mmol) was added and mixed uniformly, then 0.52 g (4 mmol) of di-n-butylamine and 0.19 g (1 mmol) of 2,2-dichloroacetophenone were added, The polymerization reaction was started by heating to 0 ° C. After 64 hours from the start of the polymerization time, the temperature of the reaction system was cooled to 0 ° C. to stop the polymerization reaction. The polymerization yield of PME-1000 was 66%. Next, the reaction solution was subjected to column purification to remove the metal complex and unreacted monomer, and then the volatile matter was removed under reduced pressure, followed by drying under reduced pressure at 60 ° C. for 5 hours to obtain poly PME-1000. When the obtained poly PME-1000 was subjected to GPC analysis, it was a monodisperse polymer having Mn = 190,000.

  Next, in an argon atmosphere, 89 g of toluene that was previously degassed was added to 0.1 g (0.12 mmol) of chloropentamethylcyclopentagenylbis (triphenylphosphine) ruthenium, and 30 g (0.16 mmol) of poly PME-1000. ), 8.0 g (77 mmol) of styrene and 0.15 g (1.2 mmol) of di-n-butylamine were added and mixed uniformly, and then heated to 100 ° C. with stirring to initiate a copolymerization reaction. 29 hours after the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C. to stop the copolymerization reaction. The polymerization yield of styrene was 32%. The reaction solution was subjected to column purification and reduced pressure purification as described above, and GPC analysis was performed on poly (St-b-PME-1000-b-St) obtained by drying under reduced pressure at 60 ° C. for 5 hours. = 210,000 monodisperse polymer.

  Next, 82 g of toluene that had been previously degassed with argon in an argon atmosphere was added 0.08 g (0.1 mmol) of chloropentamethylcyclopentagenylbis (triphenylphosphine) ruthenium, poly (St-b-PME-1000). -B-St) 20 g (0.1 mmol), HEA 7.4 g (64 mmol), di-n-butylamine 0.1 g (0.8 mmol) were added and mixed uniformly, and then heated to 80 ° C. for copolymerization reaction. Was started. 19 hours after starting the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C. to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion of HEA was 42%. The reaction solution was subjected to column purification and reduced pressure purification as described above, and GPC analysis was performed on the copolymer obtained by drying under reduced pressure at 60 ° C. for 5 hours. As a result, it was a monodisperse polymer with Mn = 240,000, When 13C NMR was measured, the ratio of the PME-1000 repeating unit moles to the total repeating unit moles in the copolymer was 80%, the St repeating unit moles ratio was 7%, and the HEA repeating unit mole ratio was 13%. %, Which is a copolymer having a poly (HEA-b-St-b-PME-1000-b-St-b-HEA) structure.

(4) Preparation of solid electrolyte membrane LiClO ₄ : 0.02 g was dissolved in 1 g of a 20 wt% THF solution of the C—B—A—B—C type block / graft copolymer prepared above, and tolylene-2,4 -0.12 g of a 10 wt% solution of diisocyanate (TDI: Wako Pure Chemical's first grade reagent) was added, and acetone (AN: Wako Pure Chemical's special grade reagent) was further added to prepare a 10 wt% concentration solution. . 1.5 g of this solution was cast on the polymer-containing positive electrode, and after removing the solvent at normal pressure and room temperature under a nitrogen stream, heated at 80 ° C. for 1 hour under a nitrogen stream, and further at 80 ° C. for 1 hour under vacuum. The resultant was heated and subjected to a crosslinking treatment with TDI, and further heated at 120 ° C. for 4 hours under vacuum to form a solid electrolyte membrane having a thickness of about 40 μm on the polymer-containing positive electrode.

(5) Charge / Discharge Test A metal Li sheet (manufactured by Furuuchi Chemical Co., Ltd., 250 μm thickness) punched through a solid electrolyte membrane positive electrode to 18 mmφ and stuck to 13 mmφ was attached, and a charge / discharge test was conducted by assembling a 2016 coin cell. The test conditions were as follows.
<Test conditions>
Voltage range: 3.0-4.2V,
Current value: 0.1 C (172 μA)
Temperature: 60 ° C
Table 1 summarizes the results of charging and discharging: 20 cycles.

(1) Synthesis of B-A-B type block graft copolymer Under an argon atmosphere, 280 g of toluene was mixed with 0.58 g (0.6 mmol) of dichlorotris (triphenylphosphine) ruthenium, methoxypolyethylene glycol monomethacrylate (Nippon Yushi ( Co., Ltd., Bremer PME-550) 120 g (178 mmol) was added and mixed uniformly, and then 0.31 g (2.4 mmol) of di-n-butylamine and 0.23 g (1.2 mmol) of 2,2-dichloroacetophenone were added. In addition, the polymerization reaction was started by heating to 80 ° C. with stirring. After 29 hours from the start of the polymerization reaction, the polymerization reaction was stopped by cooling the polymerization reaction system to 0 ° C. The polymerization rate was 82%. Subsequently, column purification of the polymerization solution was performed to remove metal complexes, unreacted monomers, and the like, and then toluene was distilled off under reduced pressure to obtain poly-methoxypolyethylene glycol monomethacrylate (abbreviated as P-PME550-20). The obtained P-PME550-20 was a polymer having a number average molecular weight (Mn) = 135800.

  Under an argon atmosphere, 468 g of toluene, 0.24 g (0.3 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, P-PME550-20: 99.5 g (1.0 mmol), styrene 17. After 6 g (169 mmol) was added and mixed uniformly, 0.26 g (2.0 mmol) of di-n-butylamine was added, and the mixture was heated to 100 ° C. with stirring to initiate the polymerization reaction. After 44 hours from the start of the polymerization reaction, the polymerization reaction was stopped by cooling the polymerization reaction system to 0 ° C. The polymerization rate of styrene was 34%. After column purification of the polymerization solution to remove the metal complex and unreacted monomer, toluene was distilled off under reduced pressure, and GPC analysis was performed on the resulting copolymer. As a result, a monodisperse polymer with Mn = 144000 was obtained. Yes, when 13C NMR was measured, it was found that the ratio of moles of PME-550 repeating units to the total number of moles of repeating units in the copolymer was 94%, and the ratio of moles of St repeating units was 6%. PME-550-b-St).

(2) A polymer solid electrolyte battery was prepared in the same manner as in Example 1 except that the copolymer obtained above was used, and a charge / discharge test was similarly conducted. The results are summarized in Table 1.

(1) Synthesis of B-A-B type block graft copolymer Under an argon atmosphere, 225 g of toluene, 0.24 g (0.25 mmol) of dichlorotris (triphenylphosphine) ruthenium, methoxypolyethylene glycol monomethacrylate (Nippon Yushi ( Co., Ltd., Blemmer PME-1000) 37.5 g (33.7 mmol), and methoxypolyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blemmer PME-400) 37.5 g (75.5 mmol) were added uniformly. After mixing, 0.13 g (1 mmol) of di-n-butylamine and 0.095 g (0.5 mmol) of 2,2-dichloroacetophenone were added and heated to 80 ° C. with stirring to initiate the polymerization reaction. After 69 hours from the start of the polymerization reaction, the polymerization reaction was stopped by cooling the polymerization reaction system to 0 ° C. The polymerization rate was 65%. Next, column purification of the polymerization solution is performed to remove metal complexes, unreacted monomers, etc., and then toluene is distilled off under reduced pressure to obtain poly-methoxypolyethylene glycol monomethacrylate (abbreviated as P-PME1000 / 400-21). It was. The obtained P-PME1000 / 400-21 was a polymer having a number average molecular weight (Mn) = 120,000, and the molecular weight distribution (Mw / Mn) was 1.45.

  Under an argon atmosphere, 123 g of toluene, 0.1 g (0.12 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, P-PME1000 / 400-21: 24.6 g (0.21 mmol), styrene After adding 6.2 g (59 mmol) and mixing uniformly, 0.06 g (2.0 mmol) of di-n-butylamine was added, and the mixture was heated to 100 ° C. with stirring to initiate the polymerization reaction. After 20 hours from the start of the polymerization reaction, the polymerization reaction was stopped by cooling the polymerization reaction system to 0 ° C. The polymerization rate of styrene was 28%. After column purification of the polymerization solution to remove the metal complex and unreacted monomer, toluene was distilled off under reduced pressure, and GPC analysis was performed on the resulting copolymer. As a result, a monodisperse polymer with Mn = 129000 was obtained. Yes, when 13C NMR was measured, the ratio of the total number of repeating units of PME-1000 and PME-400 to the total number of moles of repeating units in the copolymer was 93%, and the ratio of the St repeating unit moles was 7%. It was a copolymer having a certain poly (St-b-PME-1000 / 400-b-St) structure.

(2) A polymer solid electrolyte battery was prepared in the same manner as in Example 19 except that the copolymer obtained above was used, and a charge / discharge test was similarly conducted. The results are summarized in Table 1.

  From the above charge and discharge tests, it was found that the contact between the active material and the polymer solid electrolyte was improved by containing a homogeneous polymer that was not crosslinked to the positive electrode, and a practical battery capacity was obtained even in the solid electrolyte battery. In addition, more favorable results could be obtained by including in the positive electrode polymers having two or more polyalkylene glycol chains having different chain lengths.

Claims (37)

In a battery comprising a polymer solid electrolyte and an electrode, the polymer solid electrolyte has the formula (I)

(In the formula, R _{1 to} R ₃ each independently represents a hydrogen atom or a C 1-10 hydrocarbon group, and R ₁ and R ₃ may combine to form a ring; R _4a and R _4b Each independently represents a hydrogen atom or a methyl group, R ₅ represents a hydrogen atom, a hydrocarbon group, an acyl group or a silyl group, m represents an integer of 1 to 100, and m represents 2 In the above case, R _4a and R _4b may be the same or different.) And a repeating unit represented by formula (II)

(Wherein, R ₆ and R ₈ each independently represent a hydrogen atom or a C1~C10 hydrocarbon group,, R ₆ and R ₈ may be bonded to form a ring, R ₇ is , Hydrogen atom, C1-C10 hydrocarbon group, hydroxyl group, hydrocarbon oxy group, carboxyl group, acid anhydride group, amino group, ester group, or hydroxyl group, carboxyl group, epoxy group, acid anhydride group, and amino group Represents an organic group having at least one functional group selected from the group consisting of: R ₉ represents at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an acid anhydride group, and an amino group. A cross-linked product obtained by the reaction of a copolymer having a repeating unit represented by formula (1) and a cross-linking agent, and a copolymer containing an electrolyte salt, the electrode comprising an electrode active material, and Formula (XX)

(Wherein R _{1a to} R _3a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R _1a and R _3a may combine to form a ring, R _4a1 , R _4b1 independently represents a hydrogen atom or a methyl group, R _5a represents a hydrogen atom, a hydrocarbon group, an acyl group, or a silyl group, m1 represents any integer of 2 to 100, R _4a1 and _R4b1 may be the same or different from each other.) A block chain A11 having a repeating unit represented by formula (XXI):

(Wherein R _{6a to} R _8a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R _9a represents an aryl group), a block chain B11 having a repeating unit represented by: The battery is characterized in that the block chain C11 is an electrode including a copolymer having an arrangement of B11, A11, and C11 in this order. The battery according to claim 1, wherein the crosslinking agent is used in an amount of 0.01 to 2 mol with respect to 1 mol of the repeating unit represented by the formula (II). The battery according to claim 1, wherein the crosslinking agent is used in a range of 0.1 to 1 mol with respect to 1 mol of the repeating unit represented by the formula (II). The copolymer having repeating units represented by the formula (I) and the formula (II) contains 5 mol or more of the repeating unit represented by the formula (I). The battery described in 1. The copolymer having repeating units represented by formula (I) and formula (II) contains 5 mol or more of repeating units represented by formula (II). The battery described in 1. The number of moles of the repeating unit represented by the formula (I) is in the range of 5 to 99% with respect to the total number of moles of the repeating unit in the copolymer, and the number of moles of the repeating unit represented by the formula (II). Is in the range of 1 to 95% with respect to the total number of moles of repeating units in the copolymer. The battery according to any one of claims 1 to 6, wherein the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) are bonded by a block. The copolymer having a repeating unit represented by the formula (I) and the formula (II) further contains a repeating unit different from the formula (I) and the formula (II) derived from the polymerizable unsaturated monomer. The battery according to any one of claims 1 to 7. A repeating unit derived from a polymerizable unsaturated monomer and different from formula (I) and formula (II) is represented by formula (III)

(Wherein R _{10 to} R ₁₂ each independently represents a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group, and R ₁₃ represents an aryl group or a heteroaryl group) and formula (IV)

(Wherein, R ₁₄ to R ₁₆ each independently represent a hydrogen atom or a C1~10 hydrocarbon group,, R ₁₄ and R ₁₆ are taken together, may form a ring, R ₁₇ is 9 represents at least one repeating unit selected from repeating units represented by C1-12 alkyl group, aryl group, alicyclic hydrocarbon group, or heterocyclic group. The battery described. The battery according to claim 8 or 9, comprising 5 mol or more of a repeating unit different from the formula (I) and the formula (II) derived from a polymerizable unsaturated monomer. The repeating unit represented by the formula (I), the repeating unit represented by the formula (II), and the repeating unit different from the formula (I) and the formula (II) derived from the polymerizable unsaturated monomer are blocked. The battery according to claim 8, wherein the battery is bonded together. The total number of moles of repeating units different from the formula (I) and the formula (II) derived from the repeating unit represented by the formula (I) and the polymerizable unsaturated monomer is the total number of moles of repeating units in the copolymer. The number of moles of the repeating unit represented by the formula (II) is in the range of 1 to 95% with respect to the total number of moles of the repeating unit in the copolymer. The battery according to any one of claims 8 to 11. The number of moles of the repeating unit represented by formula (I) is in the range of 9.9 to 80% with respect to the total number of moles of repeating unit in the copolymer, and the number of repeating units represented by formula (II) The number of moles is in the range of 0.1 to 50%, and the number of moles of repeating units different from the formula (I) and formula (II) derived from the polymerizable unsaturated monomer is 19.9 to 90%. The battery according to any one of claims 8 to 12. A copolymer having a repeating unit represented by formula (I) and formula (II) has a block chain A having a repeating unit represented by formula (I) and a repeating unit represented by formula (II) A block chain B1 and a block chain B2 having a repeating unit represented by the formula (II) which may be the same as or different from the block chain B1, and the formula (III)

(Wherein R _{10 to} R ₁₂ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₁₃ represents an aryl group or a heteroaryl group). The block chain C1 and the block chain C2 having the repeating unit represented by the formula (III) which may be the same as or different from the block chain C1 are arranged in the order B1, C1, A, C2, B2. The battery according to claim 9, wherein the battery is a polymer. The battery according to claim 14, wherein the arrangement in the order of B1, C1, A, C2, and B2 is an array in which B1-C1-A-C2-B2 are combined. The repeating unit represented by formula (II) is represented by formula (IVA)

(Wherein R _{18 to} R ₂₀ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁₈ and R ₂₀ may be bonded to form a ring, and R ₂₁ represents C1 to C20) A C6 alkylene group, a C6 to C10 divalent aromatic hydrocarbon group, a C3 to C10 divalent alicyclic hydrocarbon group, or a divalent organic group in which these are combined.) (V)

(Wherein R _{22 to} R ₂₄ each independently represents a hydrogen atom or a C 1 to C 10 hydrocarbon group, and p represents an integer of 1 to 3), (VI)

(Wherein, R _181, R ₁₉₁ and R ₂₀₁ each independently represent a hydrogen atom or a C1~C10 hydrocarbon group, R ₁₈₁ and R ₂₀₁ may be combined to form a ring, R ₂₁₁ Represents a C1 to C6 alkylene group, a C6 to C10 divalent aromatic hydrocarbon group, a C3 to C10 divalent alicyclic hydrocarbon group, or a divalent organic group composed of these, and R ₂₁₂ represents a hydrogen atom. Or a C1-C4 alkyl group) or a repeating unit represented by formula (VII)

(Wherein R ₂₈₁ , R ₂₉₁ and R ₃₀₁ each independently represents a hydrogen atom or a C1-C10 hydrocarbon group, R ₂₈₁ and R ₃₀₁ may combine to form a ring, R ₃₁₁ Is a hydrogen atom or formula (VIII)

(Wherein, R ₄₁₁ represents a C1~C6 alkylene group, a divalent aromatic hydrocarbon group of C6-C10, 2 Ataiabura cyclic hydrocarbon group C3 -C10, or a divalent organic group that combines these .) Represents a functional group. The battery according to any one of claims 1 to 15, wherein the battery is a repeating unit represented by: The battery according to any one of claims 1 to 16, wherein the crosslinked body contains a urethane bond derived from a crosslinking agent. The cross-linking agent is a polyisocyanate compound containing two or more isocyanate groups in the molecule, or an epoxy compound having two or more epoxy groups in the molecule. Battery. The number average molecular weight of the copolymer containing the repeating unit represented by the formula (I) and the formula (II) is in the range of 5,000 to 1,000,000. The battery according to any one of the above. The electrolyte salt is at least one selected from the group consisting of alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and protonic acids. The battery described. The battery according to any one of claims 1 to 20, wherein the electrolyte salt is a lithium salt. Block chain C11 is represented by the formula (XXII)

(Wherein R _{10a to} R _12a each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R _13a represents an aryl group or a heteroaryl group). The battery according to any one of claims 1 to 21, wherein the battery is a block chain. The battery according to any one of claims 1 to 22, wherein the block chains B11, A11, and C11 are arranged in order of B11-A11-C11. The battery according to any one of claims 1 to 23, comprising 10 mol or more of a repeating unit represented by the formula (XX). The battery according to any one of claims 1 to 24, comprising 5 mol or more of a repeating unit represented by the formula (XXI). The battery according to any one of claims 22 to 25, comprising 5 mol or more of a repeating unit represented by the formula (XXII). 27. The battery according to claim 1, wherein m1 in the formula (XX) is an integer of 5 to 100. 27. The battery according to claim 1, wherein m1 in the formula (XX) is an integer of 10 to 100. The battery according to any one of claims 22 to 28, wherein R _13a in the formula (XXII) is an aryl group, and includes 5 or more repeating units represented by the formula (XXII). The molar ratio ((XX) / ((XXI) + C11)) of the repeating unit represented by the formula (XX) and the total of the repeating unit represented by the formula (XXI) and the repeating unit contained in the block chain C is 30. The battery according to any one of claims 1 to 29, which is in a range of 1/30 to 30/1. Molar ratio ((XX) / ((XXI) + (XXII) of the repeating unit represented by the formula (XX), the repeating unit represented by the formula (XXI), and the repeating unit represented by the formula (XXII)) The battery according to any one of claims 22 to 30, wherein))) is in the range of 1/30 to 30/1. The battery according to any one of claims 1 to 31, wherein the number average molecular weight of the copolymer having an arrangement of B11, A11, and C11 is in the range of 5,000 to 1,000,000. . The battery according to claim 1, further comprising an electrolyte salt in the electrode. The battery according to any one of claims 1 to 33, wherein the electrode contains a copolymer and an electrolyte salt in the range of 0.5 to 15% by weight. The battery according to any one of claims 1 to 34, wherein the electrode is a positive electrode and further contains a conductive material. In a battery comprising a solid polymer electrolyte and an electrode, the solid polymer electrolyte includes a crosslinked copolymer having an ion conductive site, and the electrode includes a copolymer having the same repeating unit as the copolymer. A battery characterized by that. 37. The battery according to claim 36, wherein the same repeating unit portion in the copolymer having the same repeating unit as that of the copolymer is 50 mol% or more.