JP2005100966A - High polymer solid electrolyte battery, electrode, manufacturing method for them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high polymer solid electrolyte battery having excellent thermal characteristics, physical characteristics and ion conductivity, an electrode, and a manufacturing method for them. <P>SOLUTION: (1) This high polymer solid electrolyte battery is provided with a copolymer formed by arranging a block chain A having a repeating unit expressed by the formula (1), a block chain B having a repeating unit expressed by the formula (II), and a block chain C in the order of B, A, and C, and a high polymer electrolyte containing electrolyte salt. (2) This electrode contains an electrode active material, the electrolyte salt, and the copolymer. (3) In addition, the manufacturing method for them is provided. In the formulas (I), (II), R<SB>1</SB>-R<SB>3</SB>, R<SB>6</SB>-R<SB>8</SB>express hydrogen atoms or C<SB>1</SB>-C<SB>10</SB>hydrocarbon groups, and R<SB>1</SB>-R<SB>3</SB>may form a ring by combining each other. R<SB>5</SB>expresses a hydrogen atom, a hydrocarbon, an acyl group, or a cyril group, and R<SB>4a</SB>, R<SB>4b</SB>express hydrogen atoms or methyl groups. m expresses integrals of 2-100. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer solid electrolyte battery and electrode useful for a secondary battery and the like, and a method for producing them.

  Conventionally, as a polymer solid electrolyte, an ABA type triblock copolymer obtained by copolymerizing methoxypolyethylene glycol monomethacrylate (component A) and styrene (component B) by a living anion polymerization method is used as a matrix. A polymer solid electrolyte as a base material has been proposed (Non-patent Document 1). In the matrix base material described in this document, the component A is a component that forms a PEO domain as a diffusion transport space for lithium ions. Therefore, in order to improve ion conductivity, it is preferable to increase the content of the component A in the matrix base material.

However, since the homopolymer of methoxypolyethyleneglycol monomethacrylate, which is the component A, is a liquid at room temperature even if it has a high molecular weight, in order to use the ABA type copolymer as a matrix substrate for a solid electrolyte Is limited in the content of the component A. This also means that the shape and size of the PEO domain as a lithium ion diffusion transport space are limited. In fact, the ionic conductivity of the matrix substrate at 40 ° C. was not satisfactory at 10 ⁻⁶ S / cm.

  On the other hand, as a method for improving the charge / discharge cycle characteristics of the positive electrode of a solid-state lithium secondary battery, Patent Document 1 discloses (i) an electrode made of a mixture containing a 3V class Mn oxide, a conductive additive, a binder and an organic solvent. A first step of forming a layer on the current collector, (ii) a second step of obtaining an electrode plate by removing the organic solvent by drying the electrode layer, (iii) a third step of press-molding the electrode plate, And (iv) a method for producing a composite positive electrode for a solid-state lithium secondary battery, which has a fourth step of impregnating an electrode layer with a lithium ion conductive polymer electrolyte.

  However, the composite positive electrode for a solid state lithium secondary battery obtained by the production method described in this document may not have sufficient characteristics depending on the polymer electrolyte used.

Macromol. Chem. , 190, 1069 (1989) JP 2002-157998 A

  The present invention has been made in view of the state of the prior art, a polymer solid electrolyte battery excellent in all of ionic conductivity, thermal characteristics and physical characteristics, an electrode excellent in charge / discharge cycles, and It is an object to provide these manufacturing methods.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a triblock copolymer having a block chain composed of alkoxypolyethyleneglycol mono (meth) acrylate units, which is rigid at one end or both ends such as polystyrene. When a simple block chain is arranged, solidification is possible by increasing the content of alkoxy polyethylene glycol (meth) acrylate units due to the pseudo-crosslinking effect, and a solid polymer electrolyte having high ionic conductivity is obtained. I found out that And by using this copolymer for an electrolyte or an electrode, it is possible to obtain a polymer solid electrolyte battery excellent in all of ionic conductivity, thermal characteristics and physical characteristics, and an electrode excellent in charge / discharge cycles. As a result, the present invention has been completed.

Thus, according to the first aspect of the present invention, there is provided a polymer solid electrolyte battery according to any one of the following (1) to (20).
(1) Formula (I)

(Wherein R _{1 to} R ₃ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁ and R ₃ may be bonded to form a ring, and R _4a and R _4b are 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 2 to 100, and R _4a and R _4b represent , Which may be the same or different from each other), and a block chain A having a repeating unit represented by formula (II):

(Wherein R _{6 to} R ₈ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₉ represents an aryl group) and a block chain B having a repeating unit represented by A polymer solid electrolyte battery comprising a polymer solid electrolyte in which a chain C contains a copolymer in which B, A, and C are arranged in this order, and an electrolyte salt.
(2) The block chain C 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). The solid polymer electrolyte battery according to (1), characterized in that
(3) The polymer according to (1) or (2), wherein the copolymer is a copolymer in which the block chains A to C are combined with B-A-C. Solid electrolyte battery.
(4) The polymer solid electrolyte battery according to any one of (1) to (3), wherein the degree of polymerization of the repeating unit represented by the formula (I) is 10 or more.
(5) The polymer solid electrolyte battery according to any one of (1) to (4), wherein the degree of polymerization of the repeating unit represented by the formula (II) is 5 or more.

(6) The polymer solid electrolyte battery according to any one of (2) to (5), wherein the degree of polymerization of the repeating unit represented by the formula (III) is 5 or more.
(7) The polymer solid electrolyte battery according to any one of (1) to (6), wherein m is an integer of 5 to 100 in the formula (I).
(8) The solid polymer electrolyte battery according to any one of (1) to (7), wherein in the formula (I), m is an integer of 10 to 100.

(9) R < ₁₃ > in said Formula (III) is an aryl group, The polymer solid electrolyte battery in any one of (2)-(8) characterized by the above-mentioned.
(10) Molar ratio between the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit contained in the block chain C [expressed by the formula (I) The repeating unit / (the repeating unit represented by the formula (II) + the repeating unit contained in the block chain C)] is in the range of 1/30 to 30/1. 9) Any polymer solid electrolyte battery.
(11) Molar ratio of the repeating unit represented by the formula (I) to the sum of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) [formula (I) (Repeating unit represented by formula (II) + repeating unit represented by formula (III))] is in the range of 1/30 to 30/1 ( The polymer solid electrolyte battery according to any one of 2) to (10).

(12) The polymer solid electrolyte battery according to any one of (1) to (11), wherein the copolymer has a number average molecular weight in the range of 5,000 to 1,000,000.
(13) The polymer solid electrolyte battery according to any one of (1) to (12), wherein the copolymer has a microphase separation structure.
(14) The polymer solid electrolyte battery according to any one of (1) to (13), wherein the polymer solid electrolyte has a microphase separation structure.

(15) 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 (14) ) Any polymer solid electrolyte battery.
(16) The polymer solid electrolyte battery according to any one of (1) to (14), wherein the electrolyte salt is a lithium salt.
(17) The polymer solid electrolyte battery according to any one of (1) to (16), wherein the polymer solid electrolyte contains 90% by weight or more of the copolymer.

(18) The polymer solid electrolyte battery according to any one of (1) to (17), comprising a carbon-based electrode made of a carbon-based electrode material containing the copolymer.
(19) A carbon-based electrode made of a carbon-based electrode material containing the copolymer in an amount of 1 to 15% by weight is provided as a positive electrode or a negative electrode. Molecular solid electrolyte battery.
(20) The polymer solid electrolyte battery according to any one of (1) to (19), wherein the polymer solid electrolyte is an ion conductive membrane having a network type microphase separation structure.

According to the second aspect of the present invention, any one of the following electrodes (21) to (35) is provided.
(21) Electrode active material, electrolyte salt, and formula (I)

(Wherein R _{1 to} R ₃ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁ and R ₃ may be bonded to form a ring, and R _4a and R _4b are 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 2 to 100, and R _4a and R _4b represent , Which may be the same or different, each having a repeating unit represented by formula (II)

(Wherein R _{6 to} R ₈ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₉ represents an aryl group) and a block chain B having a repeating unit represented by An electrode, wherein the chain C includes a copolymer in which B, A, and C are arranged in this order.
(22) The block chain C 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). (21) The electrode characterized by the above-mentioned.
(23) The electrode according to (21) or (22), wherein the copolymer is a copolymer in which the block chains A to C are combined with B-A-C.
(24) The electrode according to any one of (21) to (23), wherein the degree of polymerization of the repeating unit represented by the formula (I) is 10 or more.
(25) The electrode according to any one of (21) to (24), wherein the degree of polymerization of the repeating unit represented by the formula (II) is 5 or more.

(26) The electrode according to any one of (22) to (25), wherein the degree of polymerization of the repeating unit represented by the formula (III) is 5 or more.
(27) The electrode according to any one of (21) to (26), wherein m is an integer of 5 to 100 in the formula (I).
(28) The electrode according to any one of (21) to (26), wherein in the formula (I), m is an integer of any one of 10 to 100.

(29) The electrode according to any one of (22) to (28), wherein R ₁₃ in the formula (III) is an aryl group.
(30) Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit contained in the block chain C [expressed by the formula (I) The repeating unit / (the repeating unit represented by the formula (II) + the repeating unit contained in the block chain C)] is in the range of 1/30 to 30/1 (21) to (21) 29) Any electrode.
(31) Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) [formula (I) (Repeating unit represented by formula (II) + repeating unit represented by formula (III))] is in the range of 1/30 to 30/1 ( 22)-(30) any electrode.

(32) The electrode according to any one of (21) to (31), wherein the copolymer has a number average molecular weight in the range of 5,000 to 1,000,000.
(33) The electrode according to any one of (21) to (32), wherein the copolymer has a microphase separation structure.
(34) The electrode according to any one of (21) to (33), wherein the copolymer and the electrolyte salt are combined and contained in a range of 0.5 to 15% by weight.
(35) The electrode according to any one of (21) to (34), which is a positive electrode and further contains a conductive material.

According to a third aspect of the present invention, the following solid polymer electrolyte batteries (36) and (37) are provided.
(36) A solid polymer electrolyte battery comprising the electrode of (35) as a positive electrode and the electrode of any one of (21) to (34) or an alkali metal as a negative electrode.
(37) The polymer solid electrolyte battery according to (36), which is the polymer solid electrolyte battery according to any one of (1) to (20).

According to a fourth aspect of the present invention, there is provided a method for producing an electrode according to any one of (38) to (45) below.
(38) A method for producing an electrode, comprising casting or applying a solution containing a polymer and an electrolyte salt on a layer containing an electrode active material prepared on a support.
(39) The method for producing an electrode according to (38), wherein a solution containing a polymer and an alkali metal salt is cast or applied a plurality of times.
(40) The method for producing an electrode according to (38) or (39), wherein the layer containing the electrode active material contains at least one selected from an electrode active material and a polymer used as a binder and an electrolyte.

(41) The method for producing an electrode according to any one of (38) to (40), wherein the layer containing the electrode active material contains a conductive material.
(42) The layer containing the electrode active material is a layer obtained 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 solution. (38)-(41) Any one of the manufacturing method of the electrode characterized by the above-mentioned.
(43) The method for producing an electrode according to any one of (38) to (42), wherein the polymer is used as an electrolyte.

(44) The method for producing an electrode according to any one of (39) to (43), wherein a solid content concentration in the solution containing the polymer and the alkali metal salt is 0.5 to 10% by weight.
(45) The method for producing an electrode according to any one of (38) to (44), wherein the electrode according to any one of (21) to (35) is produced.

According to the fifth aspect of the present invention, there is provided a method for producing a polymer solid electrolyte battery according to any one of the following (46) to (49).
(46) On the electrode obtained by any one of the methods (38) to (45), a solution containing a polymer and an electrolyte salt is further cast or applied to form an electrolyte layer, and another electrode is provided. A method for producing a solid polymer electrolyte battery.
(47) The method for producing a solid polymer electrolyte battery according to (46), wherein a polar solvent is used as a solvent of the solution containing the polymer and the electrolyte salt, and the solution is heat-treated.
(48) The method for producing a solid polymer electrolyte battery according to (46) or (47), wherein the solid content concentration in the solution containing the polymer and the electrolyte salt is in the range of 0.5 to 30% by weight.
(49) The method for producing a polymer solid electrolyte battery according to any one of (46) to (48), wherein the polymer solid electrolyte battery according to any one of (1) to (20) is produced.

According to the sixth aspect of the present invention, the following (50) and (51) solid electrolyte production methods are provided.
(50) A method for producing a solid electrolyte by casting or coating a solution containing a polymer and an electrolyte salt on a support, and including a step of using a polar solvent as a solvent and performing a heat treatment in a state containing the solvent. A method for producing a solid electrolyte.
(51) The method for producing a solid electrolyte according to (50), wherein the solid content concentration in the solution containing the polymer and the electrolyte salt is in the range of 0.5 to 30% by weight.

The polymer solid electrolyte battery of the present invention has excellent thermal characteristics, physical characteristics and ionic conductivity at a practical level.
The electrode of the present invention has an excellent charge / discharge cycle, and is suitably used for the polymer solid electrolyte battery of the present invention.
According to the polymer solid electrolyte battery or the method for producing a solid electrolyte of the present invention, the polymer solid electrolyte battery of the present invention can be produced efficiently and simply.
According to the method for producing an electrode of the present invention, the electrode of the present invention can be produced efficiently and simply.

Hereinafter, the present invention will be described in detail.
1) Polymer solid electrolyte battery and production method thereof The polymer solid electrolyte battery of the present invention has a block chain A having a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II). Each block chain of the block chain B and the arbitrary block chain C contains a copolymer formed by arranging B, A, and C in this order, and an electrolyte salt.

(1) Copolymer The copolymer used in the polymer solid electrolyte battery of the present invention has a block chain A having a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II). Each block chain of the block chain B and the arbitrary block chain C is a copolymer in which B, A, and C are arranged in this order. Block chain B and block chain C may be the same or different.

  In the block chain A or B, having a repeating unit represented by the formula (I) or (II) means that each block chain includes other repeating units as a constituent unit in addition to the corresponding repeating unit. It means both in the absence.

  When other repeating units are included as constituent units, the polymerization mode of the repeating units represented by the formula (I) or (II) and other repeating units is not particularly limited, and random copolymerization, block copolymerization, alternating Any polymerization method such as copolymerization may be used.

  In addition, each block chain is arranged in the order of B, A, and C. Even if each block chain is directly bonded, other structural units such as a linking group and a polymer chain are sandwiched between them. Means that they may be bonded together.

  Examples of the linking group include an oxygen atom and an alkylene group, and examples of the polymer chain include a chain made of a homopolymer and a chain made of a binary or higher copolymer. The type of the copolymer constituting the polymer chain is not particularly limited, and examples thereof include a random copolymer, a block copolymer, and a gradient copolymer whose component ratio gradually changes.

  Especially, as a copolymer used for this invention, what each block chain couple | bonded with BAC and is arranged is preferable. Being bonded to B-A-C means a case where each block chain is directly bonded.

In the formula (I), R _{1 to} R ₃ 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, represents a hydrocarbon group having 1 to 10 carbon atoms such as a t-butyl group, a phenyl group, a naphthyl group, and a benzyl group. R ₁ and R ₃ may combine to form a ring. Examples of the ring include a cyclopropane ring, a cyclopentane ring, and a cyclohexane ring.

The hydrocarbon groups for R _{1 to} R ₃ may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkyl groups such as methyl group, ethyl group and n-propyl group; aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group Acyl groups such as acetyl and benzoyl groups; cyano groups; nitro groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups; alkylthio groups such as methylthio groups; alkylsulfinyl groups such as methylsulfinyl groups; An alkylsulfonyl group such as a methylsulfonyl group; an amino group optionally having a substituent such as an amino group or a dimethylamino group; an anilino group;

R _4a and R _4b each independently represent a hydrogen atom or a methyl group.
m represents an integer of 2 to 100, preferably an integer of 5 to 100, and more preferably an integer of 10 to 100. The value of m in each repeating unit may be the same or different. Further, R _4a and R _4b may be the same or different from each other.

R ₅ is a hydrogen atom; 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 And hydrocarbon groups such as naphthyl group; acyl groups such as formyl group, acetyl group, propionyl group, butyryl group and benzoyl group; silyl groups such as trimethylsilyl group and t-butyldimethylsilyl group.
The hydrocarbon group for R ₅ may have a substituent similarly to the hydrocarbon groups for R _{1 to} R ₃ .

  Specific examples of the repeating unit represented by the formula (I) include the following compounds. However, the monomer is considered to be derived from the repeating unit represented by the formula (I).

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, “Blemmer 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-butyldimethylmethylicyl Oxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol cyclohexene-1-carboxylate, methoxy polyethylene glycol - cinnamate.

These repeating units may be a single type or a combination of two or more types.
Although the degree of polymerization of the repeating unit represented by formula (I) depends on the value of m, it is preferably 10 or more, more preferably 20 or more.

In said formula (II), R < ₆ > -R < ₈ > represents a hydrogen atom or a C1-C10 hydrocarbon group each independently. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those exemplified as the hydrocarbon group of said R ₁ to R _3.

R ₉ represents an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group. These aryl groups may have a substituent such as an alkyl group or a halogen atom.

  Specific examples of the repeating unit represented by the formula (II) include the following compounds. However, the monomer is considered to be derived from the repeating unit represented by the formula (II).

  Styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, 2,4-dimethylstyrene, m-chlorostyrene, Aryl compounds such as p-chlorostyrene, 4-carboxystyrene, vinylanisole, vinylbenzoic acid, vinylaniline, vinylnaphthalene, 9-vinylanthracene.

These repeating units may be used alone or in combination of two or more.
The degree of polymerization of the repeating unit represented by the formula (II) is preferably 5 or more, and more preferably 10 or more.

  The block chain C is a block chain having an arbitrary repeating unit, and is preferably a block chain having a repeating unit represented by the formula (III).

In said formula (III), R < ₁₀ > -R < ₁₂ > represents a hydrogen atom or a C1-C10 hydrocarbon group each independently. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those exemplified as the hydrocarbon group of said R ₁ to R _3.

R ₁₃ represents an aryl group such as a phenyl group, a naphthyl group, and an anthracenyl group; or a heteroaryl group such as a 2-pyridyl group and a 4-pyridyl group, and is preferably an aryl group.
The aryl group or heteroaryl group of R ₁₃ may have a substituent such as a halogen atom or an alkyl group on an appropriate carbon atom.

  Specific examples of the repeating unit represented by the formula (III) include compounds having the following repeating units. However, the monomer is considered to be derived from the repeating unit represented by the formula (III).

  Styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene, pt-butoxystyrene, mt-butoxystyrene, 2,4-dimethylstyrene, m-chlorostyrene, p-chlorostyrene, 4-carboxystyrene, vinylanisole, vinylbenzoic acid, vinylaniline, vinylnaphthalene, 9-vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2- Vinylthiophene, 4-vinylthiophene.

These repeating units may be a single type or a combination of two or more types.
The degree of polymerization of the repeating unit represented by the formula (III) is preferably 5 or more, and more preferably 10 or more.

The copolymer of the present invention may contain a repeating unit different from the repeating units represented by the above formulas (I) to (III) (hereinafter sometimes referred to as “other repeating units”) as a constituent unit. Good. Other repeating units can also be used as the repeating unit in the block chain C when the repeating unit represented by the formula (III) is not included.
The following compounds can be illustrated as other repeating units. However, the monomer is considered to be derived from other repeating units.

  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 , Isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid such as acid 3-oxocyclohexyl, (meth) acrylic acid butyrolactone, (meth) acrylic acid mevalonic lactone;

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 and chloroprene; α, β-unsaturated carboxylic imides such as N-methylmaleimide and N-phenylmaleimide; Α, β-unsaturated nitriles such as (meth) acrylonitrile;
These repeating units may be a single type or a combination of two or more types.

Furthermore, in the copolymer used in the present invention, it has a double bond capable of copolymerization with the monomer that forms the repeating unit represented by the above formulas (I) to (III), and has a hydroxyl group, A repeating unit derived from a compound having in the molecule thereof at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an acid anhydride group, and an amino group can be included as a constituent unit.
The following compounds can be illustrated as such a repeating unit. However, the monomer is considered to be derived from such a repeating unit.

These repeating units may be a single type or a combination of two or more types.
Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit contained in the block chain C [repeating represented by the formula (I) Unit / (Repeating unit represented by formula (II) + Repeating unit contained in block chain C)] is preferably in the range of 1/30 to 30/1. If the molar ratio is less than 1/30, sufficient conductivity cannot be obtained, and if it is greater than 30/1, sufficient thermal and physical characteristics may not be obtained.

  In addition, when the block chain C has a repeating unit represented by the formula (III), the “repeating unit represented by the formula (III)” is applied instead of the “repeating unit contained in the block chain C”. be able to. That is, the molar ratio [repeating unit represented by formula (I) / (repeating unit represented by formula (II) + repeating unit represented by formula (III))] is 1/30 to 30/1. A range is preferred. If the molar ratio is less than 1/30, sufficient conductivity cannot be obtained, and if it is greater than 30/1, sufficient thermal and physical characteristics may not be obtained.

  Although the number average molecular weight measured by the gel permeation chromatography method of the copolymer used in the present invention is not particularly limited, it is preferably in the range of 5,000 to 1,000,000 in terms of polystyrene. When the number average molecular weight is less than 5,000, thermal characteristics and physical characteristics are deteriorated, and when it is greater than 1,000,000, moldability or film formability may be deteriorated.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer used in the present invention is not particularly limited, but is 1.01 in forming the microphase separation structure described later. The range of ˜2.50 is preferable, and the range of 1.01 to 1.50 is more preferable.

  The copolymer used in the present invention preferably has a microphase separation structure in the membrane structure in order to maintain high ionic conductivity as a polymer solid electrolyte, and particularly has a network type microphase separation structure. Is preferred.

(2) Copolymer Production Method When the copolymer used in the present invention contains the following formula (IV), formula (V), and a repeating unit represented by formula (III) as a block chain C, Living radical polymerization using a compound represented by the formula (VI), using a transition metal complex as a polymerization catalyst, an organic halogen compound containing one or more halogen atoms as a polymerization initiator, a living radical polymerization using a stable radical, a living anion It can manufacture using well-known methods, such as a polymerization method. Of these, 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 is preferred.

(In formulas (IV) to (VI), R _{1 to} R ₁₃ represent the same meaning as described above.)
As a method for producing the copolymer used in the present invention, more specifically,
(B) a macroinitiator containing each block chain such as a bifunctional block chain obtained by reacting a compound represented by formula (IV) with a bifunctional initiator in a living radical polymerization method; A method of producing monomers by reacting monomers constituting other block chains and then extending the block chains,
(B) A compound represented by the formula (V) is used instead of the formula (IV), a monofunctional initiator is used, and the others are performed in the same manner as in the (a), and the block chain is sequentially extended from the end to produce Method,
(C) A method of producing each block chain or a part of each block chain by a coupling reaction after polymerizing in a predetermined sequence can be exemplified.

  Living radical polymerization can be performed using a transition metal complex as a polymerization catalyst and an organic halogen compound having one or more halogen atoms in the molecule as a polymerization initiator.

  As the central metal composing the transition metal complex, periodic table 7th to 11th elements such as manganese, rhenium, iron, ruthenium, rhodium, nickel, copper, etc. (According to the periodic table described in (1993)). Of these, ruthenium is preferable.

  Although it does not specifically limit as a ligand which coordinates to these metals and forms a complex, For example, C18-54 triaryl phosphine, such as triphenylphosphine and trinaphthylphosphine, triethylphosphine, tributylphosphine, etc. A triaryl phosphite having 3 to 18 carbon atoms, a triaryl phosphite such as triphenyl phosphite, a halogen atom such as diphenylphosphinoethane, iodine, bromine, chlorine, carbon monoxide, a hydrogen atom, cyclopentadiene, cyclohexadiene, Cyclooctadiene, cyclooctatetraene, indene, norbornadiene, benzene, cymene, phenol, 4-isopropyltoluene, cyclopentadienyltoluene, indenyltoluene, salicylidene, 2-methylpentene, 2-butene, allene , It may be mentioned furan, carboxylic acid, etc. Preferred examples. Nitrogen-containing ligands and chalcogenides are also useful.

  Among the ligands exemplified above, hydrocarbon ligands include various substituents such as alkyl groups (C1-C4 alkyl groups such as methyl groups and ethyl groups), alkenyl groups (vinyl groups, allyl groups, etc.). Alkynyl group, alkoxy group (C1-C4 alkoxy group such as methoxy group), alkoxycarbonyl group (C1-C4 alkoxy-carbonyl group such as methoxycarbonyl group), acyl group (acetyl) C2-C5 acyl group such as a group), acyloxy group (C2-C5 acyloxy group such as formyl group, acetyloxy group, etc.), carboxyl group, hydroxyl group, amino group, amide group, imino group, nitro group, cyano group , A thioester group, a thioketone group, a thioether group, a halogen atom (chlorine, bromine, etc.) and the like. Examples of the hydrocarbon ligand having a substituent include a cyclic hydrocarbon ligand which may be substituted with 1 to 5 methyl groups such as a pentamethylcyclopentadienyl group.

In addition to the ligands exemplified above, transition metal complexes include hydroxyl groups, alkoxy groups (methoxy, ethoxy, propoxy, butoxy groups, etc.), acyl groups (acetyl, propionyl groups, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl). Group), β-diketone group such as acetylacetonate, acetylacetate, etc., β-ketoester group, pseudohalogen group [CN, thiocyanate (SCN), selenocyanate (SeCN), tellurocyanate (TeCN), SCSN ₃ , OCN, ONC, azide (N ₃ ), etc.], oxygen atom, H ₂ O, nitrogen-containing compound [NH ₃ , NO, NO ₂ , NO ₃ , ethylenediamine, diethylenetriamine, tributylamine, 1,3-diisopropyl-4, 5-dimethylimidazol-2-ylidene, pyridine Phenanthroline, diphenanthroline and substituted phenanthroline, 2,2 ': 6', 2 "-terpyridine, pyridineimine, bridged aliphatic diamine, 4-4'-di (5-nonyl) -2,2'-bipyridine, thiocyanate , O, S, Se, Te coordinated bipyridine, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) alkylpyridine, ethylenediaminedipyridine, tri (pyridinylmethyl) amine, etc.] You may do it.

  Typical examples of the transition metal complex include a transition metal complex having ruthenium as a central metal, dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (trialkylphosphine) p-cymeneruthenium, Dichloro-di (tricymenephosphine) styrylruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzeneruthenium, dichlorop-cymeneruthenium, dichloro (norbornadiene) ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, chlorocyclopentadienylbis (triphenylphosphine) ) Ruthenium, chloroindenylbis (triphenylphosphine) ruthenium, dihydrotetra (triphenylphosphine) ruthenium, etc., especially dichlorotris (triphenylphosphine) ruthenium or chloroindenylbis (triphenylphosphine) ruthenium, dihydro Preferred examples include tetrakis (triphenylphosphine) ruthenium.

  Furthermore, as other transition metal complexes, di (triphenylphosphine) iron dichloride, di (tributylamino) iron dichloride, triphenylphosphine trichloride, (1-bromo) ethylbenzene-triethoxyphosphine-iron dibromide (1-bromo) ethylbenzene-triphenylphosphine-iron dibromide, (1-bromo) ethylbenzene- [4-4′-di (5-nonyl) -2,2′-bipyridine] iron dibromide, ( 1-bromo) ethylbenzene-tri-n-butylamino-iron dibromide, (1-bromo) ethylbenzene-tri-n-butylphosphine-iron dibromide, tri-n-butylphosphine-iron dibromide, [ 4-4′-di (5-nonyl) -2,2′-bipyridine] iron dibromide, tetraalkylammonium iron (III) trihalide, dicarbonylcyclopentadieny Iron (II) iodide, dicarbonylcyclopentadienyl iron bromide (II), dicarbonylcyclopentadienyl iron chloride (II), dicarbonyl indenyl iron iodide (II), dicarbonyl indenyl iron bromide (II), dicarbonyl indenyl iron chloride (II), dicarbonyl fluorenyl iron iodide (II), dicarbonyl fluorenyl iron bromide (II), dicarbonyl fluorenyl iron chloride (II), 1 , 3-diisopropyl-4,5-dimethylimidazol-2-ylidene iron chloride, 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene iron bromide, and the like;

Dicarbonylcyclopentadienyl ruthenium iodide (II), dicarbonylcyclopentadienyl ruthenium bromide (II), dicarbonylcyclopentadienyl ruthenium chloride (II), dicarbonyl indenyl ruthenium iodide (II), di Carbonyl indenyl ruthenium bromide (II), dicarbonyl indenyl ruthenium chloride (II), dicarbonyl fluorenyl ruthenium iodide (II), dicarbonyl fluorenyl ruthenium bromide (II), dicarbonyl fluorenyl chloride Ruthenium complexes such as ruthenium (II), dichloro-di-2,6-bis [(dimethylamino) -methyl] (μ-N ₂ ) pyridine ruthenium (II); carbonylcyclopentadienyl nickel iodide (II), Carbonyl cyclopentadienyl nickel bromide (II), carbonylcyclopentadienyl nickel chloride (II), carbonyl indenyl nickel iodide (II), carbonyl indenyl nickel bromide (II), carbonyl indenyl nickel chloride (II), carbonyl fluorenyl iodide Nickel (II), carbonyl fluorenyl nickel iodide (II), carbonyl fluorenyl nickel bromide (II), carbonyl fluorenyl nickel chloride (II), o, o'-di (dimethylaminomethyl) phenyl halogen Nickel bromide, di-triphenylphosphine nickel dibromide, di (tri-n-butylamino) nickel dibromide, 1,3-diaminophenyl nickel bromide, di (tri-n-butylphosphine) nickel dibromide, tetra Nickel complexes such as (triphenylphosphine) nickel;

  Tricarbonylcyclopentadienyl molybdenum iodide (II), tricarbonylcyclopentadienyl molybdenum bromide (II), tricarbonylcyclopentadienyl molybdenum chloride (II), di-N-aryl-di (2-dimethylaminomethyl) Phenyl) lithium molybdenum, di-N aryl- (2-dimethylaminomethylphenyl) -methyl-lithium molybdenum, di-N aryl- (2-dimethylaminomethylphenyl) -trimethylsilylmethyl-lithium molybdenum, di-N-aryl- (2- Molybdenum complexes such as dimethylaminomethylphenyl) -p-tolyl-lithium molybdenum; tricarbonylcyclopentadienyl tungsten iodide (II), tricarbonylcyclopentadienyl tungsten bromide (II), tricarbonyl Tungsten complexes such as clopentadienyl tungsten chloride (II); cobalt complexes such as dicarbonylcyclopentadienyl cobalt (I); tricarbonylcyclopentadienyl manganese (I), tricarbonyl (methylcyclopentadienyl) manganese Manganese complexes such as (I); rhenium complexes such as tricarbonylcyclopentadienylrhenium (I), dioxobis (triphenylphosphine) rhenium iodide, rhodium complexes such as tri (triphenylphosphine) rhodium chloride; triphenylphosphine diacetyl Palladium complexes such as palladium; diphenanthroline, substituted phenanthroline, 2,2 ′: 6 ′, 2 ″ -terpyridine, pyridineimine, bridged aliphatic diamine, alkylbipyridinylamine, alkyl-substituted tripyridine, Copper complexes having (alkylamino) alkylpyridine, iminodipyridine, ethylenediaminedipyridine, tris (pyridinylmethyl) amine, etc. as ligands; acetyl [4-4′-di (5-nonyl) -2,2′-bipyridine ], Hexafluorophosphine-di [4-4′-di (5-nonyl) -2,2′-bipyridine] copper, thiocyanate copper, bipyridine copper coordinated with O, S, Se, Te, etc. Among them, dicarbonylcyclopentadienyl iron iodide (I), dicarbonylcyclopentadienyl ruthenium iodide (II), carbonylcyclopentadienyl nickel iodide (II) These transition metal complexes can be used alone or in combination of two or more.

  The organic halogen compound contains 1 to 4 or more halogen atoms, and is used as a polymerization initiator that initiates polymerization by generating radical species by acting with a transition metal complex. The organic halogen compound to be used is not particularly limited, and examples thereof include a halogen compound represented by the following formula (VII) or (VIII). Such organic halogen compounds can be used singly or in combination.

In formulas (VII) and (VIII), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic group containing a hetero atom.
R ₁₆ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an organic group containing a hetero atom.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, or organic group containing a hetero atom represented by R _{14 to} R ₁₆ may have a substituent.
Z ₁ represents a halogen atom or an organic group containing a halogen atom, and Z ₂ represents the same meaning as Z ₁ , R ₁₄ or R ₁₅ .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom, a bromine atom or an iodine atom is preferable.
Examples of the alkyl group include C1-C12 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
Examples of the cycloalkyl group include C4-12 cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, and a C4-C8 cycloalkyl group is preferable.

Examples of the aryl group include C6-C12 aryl groups such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
Examples of the aralkyl group include C7-C14 aralkyl groups such as a benzyl group and a phenethyl group.
The organic group containing a heteroatom is an organic group containing at least one heteroatom (a heteroatom such as nitrogen, oxygen or sulfur), such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or a butoxycarbonyl group. Aliphatic C1-C10 alkoxycarbonyl group; C6-C12 aryloxycarbonyl group such as phenoxycarbonyl group, aliphatic C2-C10 acyloxy group such as acetoxy group, propionyloxy group; C6-C12 arylcarbonyloxy group such as benzoyloxy group Aliphatic C1-C10 acyl group such as formyl group and acetyl group; C6-C12 aryl-carbonyl group such as benzoyl group; aliphatic C1-C10 alkoxy group such as methoxy group and ethoxy group; phenoxy group, 1-naphthyloxy Group, 2-naphthyloxy C6-C12 aryloxy groups such as groups; carboxyl groups; hydroxyl groups; nitrogen-containing functional groups such as amino groups, amide groups, imino groups, cyano groups, and nitro groups; sulfur-containing functional groups such as thioester groups, thioketone groups, and thioether groups Group; etc. are mentioned.
Further, R ₁₄ and R ₁₅ other than the halogen atom may have the same substituent as the substituent of the hydrocarbon ligand.

  Among these, the halogenated hydrocarbon represented by the formula (VII), the halogenated ester (halogen-containing ester), the halogenated ketone (halogen-containing ketone), the halogen-containing nitrile, and the sulfonyl represented by the formula (VIII). Halides (halogenated sulfonyl compounds) and the like are preferred.

  Examples of the halogenated hydrocarbon include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, n-propyl bromide, n-propyl iodide, isopropyl chloride, Monohalo C1-C12 alkanes such as isopropyl bromide, isopropyl iodide, t-butyl chloride, t-butyl bromide, t-butyl iodide; dichloromethane, dibromomethane, diiodomethane, 1,1-dichloroethane, 1,1-dibromo Ethane, 1,1-diiodoethane, 1-bromo-1-chloroethane, 2,2-dichloropropane, 2,2-dibromopropane, 2,2-diiodopropane, 2-chloro-2-iodopropane, 2-bromo Dihalo C1-C12 alkanes such as 2-iodopropane; cyclohexyl chloride, cyclooctyl C5-C10 cycloalkyl halides such as rides; C6-C14 aryl halides such as chlorobenzene and dichlorobenzene; benzyl chloride, benzyl bromide, benzyl iodide, benzhydryl chloride, benzhydryl bromide, 1-phenylethyl chloride, 1-phenyl And C7-C14 aralkyl halides such as ethyl bromide, 1-phenylethyl iodide, xylylene dichloride, xylylene dibromide, xylylene diiodide, dichlorophenylmethane, dichlorodiphenylmethane, and the like.

Examples of halogen-containing esters include methyl dichloroacetate, methyl trichloroacetate, methyl α-bromophenylacetate, ethyl 2-bromo-2-methylpropionate, hydroxyethyl 2-bromo-propionate, glycidylmethyl 2-bromo-propionate, 2-bromo-propionic acid propenyl, vinyl chloroacetate, bromolactone, 2-bromo-propionic acid-p-carboxylphenol ethyl, 2-chloroisobutyric acid methyl, 2-chloroisobutyric acid ethyl, 2-bromoisobutyric acid, 2-bromoiso C1-C10 alkyl esters, substituted alkyl esters and alkenyl esters of halogen-containing C2-C12 monocarboxylic acids such as ethyl butyrate, methyl 2-iodoisobutyrate, ethyl 2-iodoisobutyrate;
Dimethyl 2-chloro-2-methylmalonate, diethyl 2-chloro-2-methylmalonate, dimethyl 2-bromo-2-methylmalonate, diethyl 2-bromo-2-methylmalonate, 2-iodo-2- C1-C10 alkyl esters of halogen-containing C1-C14 polyvalent carboxylic acids such as dimethyl methylmalonate, diethyl 2-iodo-2-methylmalonate, dimethyl 2-bromo-2,4,4, trimethyl-glutarate;
Examples thereof include halogen-containing C2-C12 carboxylic acids such as dichloroacetic acid, dibromoacetic acid, 2-chloroisobutyric acid, and 2-bromoisobutyric acid.

  Examples of halogen-containing ketones include halogenated C1-C10 alkyl-C1-C10 alkyl ketones such as 2-chloroacetone, 1,1-dichloroacetone, ethylchloromethylketone, 1-bromoethylethylketone; 2,2-dichloroacetophenone And halogenated C1-C10 alkyl-C6-C12 aryl ketones such as 2-bromoisobutyrophenone.

  Examples of the halogen-containing nitrile include 2-bromopropionitrile, and benzyl thiocyanate can also be used as its series.

In the present invention, in addition to the halogen compound represented by the formula (VII), an organic halogen compound containing 3 to 4 halogen atoms can also be used as an initiator. Those containing three halogen atoms include trihalo C1-C12 alkanes such as chloroform; C7-14 aralkyl halides such as trichlorophenylmethane; C1-C10 alkyls of halogen-containing C2-C12 monocarboxylic acids such as acetyltrichloromethane. Examples of the ester include halogenated C1-C10 alkyl-C1-C10 alkyl ketone such as 1,1,1, -trichloroacetone. Examples of those containing 4 halogen atoms include tetrahalo C1-C12 alkanes such as carbon tetrachloride and bromotrichloromethane.
Also, those containing more than 4 halogen atoms, such as trifluorotrichloride ethane, can be used.

  Examples of the sulfonyl halide represented by the formula (VIII) include methanesulfonyl chloride, methanesulfonyl bromide, methanesulfonyl iodide, chloromethanesulfonyl chloride, chloromethanesulfonyl bromide, chloromethanesulfonyl iodide, dichloromethanesulfonyl chloride, odor Dichloromethanesulfonyl iodide, dichloromethanesulfonyl iodide, bromomethanesulfonyl chloride, bromomethanesulfonyl bromide, bromomethanesulfonyl iodide, dibromomethanesulfonyl chloride, dibromomethanesulfonyl bromide, dibromomethanesulfonyl iodide, iodomethanesulfonyl chloride, bromide Iodomethanesulfonyl, iodomethanesulfonyl iodide, diiodomethanesulfonyl chloride, diiodomethanesulfonyl bromide, diiodomethanesulfonyl iodide, trichloride Aliphatic sulfonyl halides such as loromethanesulfonyl; benzenesulfonyl chloride, benzenesulfonyl bromide, benzenesulfonyl iodide, p-methylbenzenesulfonyl chloride, p-methylbenzenesulfonyl bromide, p-methylbenzenesulfonyl iodide, p- Chlorobenzenesulfonyl, p-chlorobenzenesulfonyl bromide, p-chlorobenzenesulfonyl iodide, p-methoxybenzenesulfonyl chloride, p-methoxybenzenesulfonyl bromide, p-methoxybenzenesulfonyl iodide, p-nitrobenzenesulfonyl chloride, p- Nitrobenzenesulfonyl, p-nitrobenzenesulfonyl iodide, p-benzenebenzene chloride, p-carboxylbenzenesulfonyl chloride, p-aminodiazobenzenesulfonyl chloride, chloride 2,5-dichlorobenzenesulfonyl, -2,5-dimethoxybenzenesulfonyl chloride, 2-hydroxy-3,5-dichlorobenzenesulfonyl chloride, 1-naphthalenesulfonyl chloride, 2-naphthalenesulfonyl chloride, (5-amino- 2-Naphthalene) sulfonyl, 1,4-disulfonylbenzene chloride, 1,4-disulfonylbenzene dibromide, 1,4-disulfonylbenzene diiodide, 2,6-disulfonylnaphthalene dichloride, dibromide And aromatic sulfonyl halides such as 2,6-disulfonylnaphthalene and 2,6-disulfonylnaphthalene diiodide.

  Furthermore, as other halogen compounds having a hetero atom, aliphatic, alicyclic or aromatic halogenated C1-C10 alcohols such as 2,2-dichloroethanol and 2,2-dibromoethanol; dichloroacetonitrile, dibromoacetonitrile and the like Halogenated nitriles such as halogenated acetonitrile, halogenated aldehydes, halogenated amides, and the like.

  In the living radical polymerization method, a Lewis acid and / or an amine can be used as an activator for promoting radical polymerization by acting on a metal complex. The Lewis acids and amines can be used singly or in combination of two or more.

  The kind of Lewis acid is not particularly limited, and various Lewis acids such as compounds represented by the following formula (IX) or (X) can be used.

In the formulas (IX) and (X), M ₁ represents a periodic table group 3 element or a periodic table group 13 element, and M ₂ represents a periodic table group 4 element or a periodic table group 14 element.
Specific examples of the M ₁ include periodic group 3 elements such as scandium (Sc) and yttrium (Y); periods such as boron (B), aluminum (Al), gallium (Ga), and indium (In). Table 13 group elements. Among these, Sc, B, and Al are preferable, and Sc and Al are more preferable.

Specific examples of the M ₂ include periodic group 4 elements such as titanium (Ti), zirconium (Zr), and hafnium (Hf); periods such as silicon (Si), tin (Sn), and lead (Pb). Table 14 group elements. Among these, Ti, Zr, Sn, etc. are preferable.

R _{17 to} R ₂₀ each independently represent a halogen atom; a C1-C12 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group; cyclopentyl C4-C12 cycloalkyl groups such as a group, cyclohexyl group, cyclooctyl group; C6-C12 aryl groups such as phenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group; benzyl group, phenethyl group, etc. C7-C14 aralkyl group; C1-C12 alkoxy group such as methoxy group, ethoxy group and isopropoxy group; C4-C12 cycloalkyloxy group such as cyclopentyloxy group, cyclohexyloxy group and cyclooctyloxy group; C6 such as phenoxy group -C12 aryloxy group; benzyloxy group, phenethyloxy group The C7-C14 aralkyloxy group; represents a like.

The substituents R _{17 to} R ₂₀ other than the halogen atom may have the same substituent as the substituent of the hydrocarbon ligand. For example, the aryloxy group may have one or more substituents such as a C1-C5 alkyl group on the aromatic ring. Specific examples of such a substituted aryloxy group include 2-methyl Phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-dimethylphenoxy group, 2,6-diethylphenoxy group, 2 , 6-diisopropylphenoxy group, 2,6-di-n-butylphenoxy group, 2,6-di-t-butylphenoxy group, and the like.
Among these, as R < ₁₇ > -R < ₂₀ >, a halogen atom, an alkyl group, an alkoxy group, etc. are preferable.

  Specific examples of the compound represented by the formula (IX) include aluminum alkoxide [aluminum triethoxide, aluminum triisopropoxide, aluminum tris-butoxide, aluminum tri-t-butoxide, aluminum triphenoxide, and the like. C1-C4 alkoxide or aryloxide of methylaluminum bis (2,6-di-t-butylphenoxide), ethylaluminum bis (2,6-di-t-butylphenoxide), methylaluminum bis (2,6-dioxy) Alkyl aluminum aryloxide such as -t-butyl-4-methylphenoxide)], aluminum such as aluminum halide (aluminum trihalide such as aluminum trichloride, aluminum tribromide, aluminum triiodide, etc.) Lewis acids; the aluminum-based Lewis acid, scandium-based Lewis acids that correspond to (scandium alkoxides such as scandium triisopropoxide, Three scandium trichloride, tribromide, scandium three scandium halides such as scandium iodide, etc.) and the like.

  Specific examples of the compound of the formula (X) include titanium alkoxide (titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra-t). -Butoxide, titanium tetraphenoxide, chlorotitanium triisopropoxide, dichlorotitanium diisopropoxide, trichlorotitanium isopropoxide, etc.); titanium such as titanium halide (titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc.) Lewis acid corresponding to the titanium Lewis acid (zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetra t-butoxide, etc.) Zirconium alkoxide, zirconium tetrachloride, zirconium tetrabromide, zirconium halides such as zirconium tetraiodide); tin-based Lewis acids corresponding to the titanium-based Lewis acids (tin alkoxides such as tin tetraisopropoxide, tin tetrachloride, And tin halides such as tin tetrabromide and tin tetraiodide).

  Among these, preferable Lewis acids include metal compounds (particularly metal alkoxides) selected from aluminum, scandium, titanium, zirconium and tin, such as aluminum alkoxides (aluminum triethoxide, aluminum triisopropoxide, aluminum). Tris-butoxide, aluminum tri-t-butoxide, etc.), scandium alkoxide (scandium triisopropoxide, etc.), titanium alkoxide (titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium) Tetra-toxide, titanium tetraphenoxide, etc.), zirconium alkoxide (zirconium tetraisopropoxide, etc.), tin alkoxide (tin tetraisopoxide, etc.) Pokishido) or the like.

  Examples of the amines include secondary amines, tertiary amines, nitrogen-containing aromatic heterocyclic compounds, nitrogen-containing compounds, and the like. Secondary amines and tertiary amines are preferred.

Specific examples of the secondary amine include dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, pyrrolidine, piperidine, 2,2,6,6-tetramethylpiperidine, Examples include piperazine and morpholine.
Specific examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, N, N, N ′, N′-tetramethylethylenediamine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] unde-7-cene and the like.

Moreover, the compound which has at least 2 or more chosen from a primary amine part, a secondary amine part, and a tertiary amine part in the same molecule can also be used.
Specific examples of such compounds include diethylenetriamine, triethylenetetramine, tetraethylpentamine, and 4- (2-aminoethyl) piperidine.

  The ratio of the transition metal complex to the Lewis acid or amine is the former / the latter = 0.05 / 1 to 10/1 (molar ratio), preferably about 0.1 / 1 to 5/1 (molar ratio). .

Living radical polymerization can also be performed using stable radicals.
Examples of the stable radical include a mixture of a stable free radical compound and a radical polymerization initiator, or various alkoxyamines.

  Stable free radical compounds are those that exist as stable free radicals alone at room temperature or under polymerization conditions, and that can react with a growing terminal radical to form a re-dissociable bond during the polymerization reaction. .

  Examples of stable free radical compounds include 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-amino-2,2,6,6-tetramethyl-1-piperidinyl. Oxy, 4-hydroxy-2,2,6,6-tetramethyl-1-piperdinyloxy, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, 4,4 ′ -Dimethyl-1,3-oxazolin-3-yloxy, 2,2,5,5-tetramethyl-1-pyrosinyloxy, di-t-butyl nitroxide, 2,2-di (4-t-octylphenyl) -1 -The compound etc. which produce | generate one or more nitroxide radicals, such as picryl hydrazyl, and a hydrazinyl radical are mentioned.

The radical polymerization initiator used is not particularly limited as long as it is a compound that decomposes to generate free radicals. For example, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), diacyl peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, etc. Ketone peroxides, peroxyketals such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxides such as cumene hydroperoxide, dicumyl peroxide And organic peroxides of peroxyesters such as dialkyl peroxides such as t-butyl peroxypivalate and t-butyl peroxybenzoate. Moreover, you may use together the well-known polymerization accelerator used in combination with organic peroxides, such as a dimethylaniline and cobalt naphthenate.
These radical polymerization initiators are generally used in an amount of 0.05 to 5 mol, preferably 0.2 to 2 mol, per 1 mol of the above-mentioned stable free radical compound.

Examples of alkoxyamines include radical polymerization handbook, page 107 (1999) NTS, J. MoI. Am. Chem. Soc. , 121 , 3904 (1999), and the like, and the following compounds are particularly preferred.

As a method for producing a copolymer by the living radical polymerization method, specifically,
(1) After the conversion rate of the first monomer reaches 100%, the second monomer is added to complete the polymerization, and the monomer for obtaining the block copolymer by repeating this is obtained. A sequential addition method,
(2) 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 has been reached, and random parts between the block chains. To obtain a gradient copolymer in which
(3) Even if the conversion rate of the first monomer does not reach 100%, the reaction is stopped once the target degree of polymerization or molecular weight has been reached, the polymer is taken out of the system, and the resulting polymer is A method of obtaining a block copolymer by intermittently advancing copolymerization by adding other monomers as an initiator,
Etc. can be illustrated.

  The polymerization method is not particularly limited, and a conventionally known method can be employed. For example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be adopted, and a solution polymerization method is particularly preferable.

  When employing the solution polymerization method, the solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; aliphatic carbonization such as hexane and octane. Hydrogens; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Sulfoxides such as sulfoxide; alcohols such as methanol and ethanol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; These solvents can be used alone or in combination of two or more.

  The polymerization is usually carried out under reduced pressure or in an atmosphere of an inert gas such as nitrogen gas or argon gas, at a polymerization temperature of 0 to 200 ° C., preferably 40 to 150 ° C.

  In the living anion polymerization method, a polymerization temperature of −100 to +50 is usually used in an organic solvent under reduced pressure or in an atmosphere of an inert gas such as nitrogen gas or argon gas using an alkali metal or an organic alkali metal as a polymerization initiator. It can be carried out at ° C, preferably -100 to -20 ° C.

Examples of the alkali metal used include lithium, potassium, sodium, cesium and the like.
As the organic alkali metal to be used, alkylated products, allylated products, arylated products and the like of the above alkali metals can be used. Specifically, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, α-methylstyrene dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium and the like can be mentioned.

  Organic solvents used in the living anion polymerization method include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; cyclic hydrocarbons such as cyclohexane and cyclopentane; acetone and methyl ethyl ketone And organic solvents usually used in anionic polymerization such as tones such as cyclohexanone; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and anisole; amides such as hexamethylphosphoramide;

  For the purpose of controlling the copolymerization reaction, known additives such as alkali metal salts and / or alkaline earth metal salts of mineral acids such as lithium chloride may be added to the reaction system.

  In addition, when employing a living anion polymerization method or a living radical method and using a compound having an active hydrogen such as a hydroxyl group or a carboxyl group in the molecule, silylation, acetalization, benzyloxycarbonylation may be performed as necessary. The active hydrogen is protected by a known protection reaction such as (BOC conversion), and then subjected to a polymerization reaction. After the polymerization, a deprotection reaction is performed with an acid, an alkali, or the like to produce the target product with higher yield. There are cases where it is possible.

Tracking of the copolymerization reaction and confirmation of the completion of the reaction can be easily performed by using known analysis means such as gas chromatography, liquid chromatography, gel permeation chromatography, membrane osmotic pressure method, and NMR.
After completion of the copolymerization reaction, the desired copolymer can be obtained by applying a normal separation and purification method such as column purification or precipitation.

(3) Polymer solid electrolyte The polymer solid electrolyte of the polymer solid electrolyte battery of the present invention is characterized by containing the above-mentioned copolymer and an electrolyte salt.
The said copolymer can be used individually by 1 type or in mixture of 2 or more types from which a structural unit differs.
In the copolymer, the block chain A has a repeating unit represented by the formula (I), and thus can be said to be a polymer segment (P1) having ion conductivity, and the block chain B is represented by the formula (II). It is said that it is a polymer segment (P2) having no ionic conductivity because it contains a repeating unit represented by formula (III), and a block chain C containing a repeating unit represented by formula (III) which is a preferred embodiment is also an ion. It can be said that the polymer segment (P2) has no conductivity, and when the block chain is represented by each polymer segment, the copolymer is a polymer arranged in the order of P2, P1, and P2. It can be said.

The polymer solid electrolyte contains an electrolyte salt in addition to the copolymer.
The electrolyte salt to be used is not particularly limited as long as it is an electrolyte containing an ion desired to be a carrier by electric charge, but it is desirable that the dissociation constant in the polymer solid electrolyte obtained by curing is large.

Examples of the electrolyte salt include alkali metal salts, quaternary ammonium salts such as (CH ₃ ) ₄ NBF ₆ ; quaternary phosphonium salts such as (CH ₃ ) ₄ PBF ₆ ; transition metal salts such as AgClO ₄ ; hydrochloric acid, And protonic acids such as perchloric acid and borohydrofluoric acid. These electrolyte salts can be used alone or in combination of two or more.

  Among these, in the present invention, an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt is preferable, and an alkali metal salt is more preferable.

Specific examples of the alkali metal salt 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) 2, LiCH 2 (CF} 3 SO 2), LiC 2 F 5 SO 3, LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2), LiB (CF 3 SO 2) 2, LiPF 6 _{,, LiSbF 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, KPF 6, Mg (ClO 4) 2, Mg (BF 4) 2 Hitoshigakyo Is, lithium salts are particularly preferred.

  The addition amount of the electrolyte salt is usually in the range of 0.005 to 80 mol%, preferably in the range of 0.01 to 50 mol% with respect to the alkylene oxide unit in the copolymer.

  The polymer electrolyte can be produced by adding and mixing (compositing) an electrolyte salt with the above-described copolymer. There is no particular limitation on the method of adding and mixing (combining), for example, a method in which the copolymer and the electrolyte salt are dissolved in a suitable solvent such as tetrahydrofuran, methyl ethyl ketone, acetonitrile, ethanol, dimethylformamide, the copolymer and the electrolyte salt, and the like. And the like, and a method of molding the polymer solid electrolyte into a sheet shape, a film shape, a film shape or the like is preferable. When this method is adopted, the degree of freedom of the processed surface is widened, which is a great advantage in application.

  As a means for producing a solid polymer electrolyte such as a sheet, the polymer solid electrolyte is applied 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. There is a method of forming a film and then removing the support.

  Examples of the method for forming a film of the polymer solid electrolyte on the support include a method in which a solution containing a polymer and an electrolyte salt is cast or coated on the support and then molded.

  The solvent used for the solution is preferably a polar solvent. The polar solvent is not particularly limited as long as it has polarity. Specifically, acetonitrile, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, chloroform, N-methylpyrrolidone, methanol and the like may be exemplified. it can.

  The solid content concentration of the solution to be used is not particularly limited, but is preferably in the range of 0.5 to 30% by weight. If it is less than 0.5% by weight, the concentration is too dilute to obtain a molded product in a small number of steps, and if it is more than 30% by weight, the film thickness may not be controlled.

  In addition, after casting or coating, it is necessary to remove the solvent by a method such as normal pressure or vacuum distillation, heat drying, or the like, but it is preferable to perform heat treatment in a state containing at least the solvent. Here, the state including the solvent is a state before the solvent is completely removed, and is 10 to 50% by weight, preferably 15 to 30% by weight, based on the solid content in the cast or applied solution. In this range, the solvent remains. By performing the heat treatment with the solvent remaining, a microphase separation structure can be formed uniformly. The heating temperature is not particularly limited, but is preferably near or above the glass transition temperature.

  The polymer solid electrolyte obtained as described above functions as an ion conductive membrane, and the membrane includes the polymer segment (P1) having the polymer segment ion conductivity and the polymer segment (P2) having no ion conductivity. ), A polymer containing a polymer, wherein a microphase separation structure is formed in the film, and a microdomain composed of P1 and a microdomain composed of P2 exist.

  The microphase separation structure in the ion conductive membrane is preferably a network type microphase separation structure. By having such a structure in the film, ionic conductivity, physical characteristics, and thermal characteristics, particularly film strength can be improved.

(4) Polymer solid electrolyte battery The polymer solid electrolyte battery of the present invention comprises the polymer solid electrolyte. 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 support by various coating means such as a roll coater method, curtain coater method, spin coat method, dip method, cast method, and the other electrode is disposed. And can be manufactured.

  The polymer solid electrolyte battery of the present invention has excellent thermal characteristics, physical characteristics and ionic conductivity at a practical level.

2) Electrode and production method thereof (1) Electrode The electrode of the present invention is characterized by containing an electrode active material, an electrolyte salt, and the copolymer described above. Further, when the electrode is a positive electrode, it is preferable that the electrode further contains a conductive material.

The electrode active material used in the present invention is not particularly limited, and a conventionally known electrode active material can be used. Specifically, simple metals such as metallic lithium, metallic silver and metallic zinc; alloys such as Li-Al; various carbon-based materials obtained by 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 and LiCoO ₂ ; chalcogenides such as TiS ₂ , TiS ₃ , MoS ₂ , CuCo ₂ S ₄ , VSe ₂ , NbSe ₂ CrS ₂ and NbSe ₃ ; Ag ₂ CrO ₄ , Such as silver oxyacids such as Ag ₂ MoO ₄ , AgIO ₃ , Ag ₂ P ₂ O ₇ , polyaniline, polypyrrole, polythiophene, poly-p-phenylene, etc. Examples thereof include conjugated polymers.

The electrolyte salt to be used can be exemplified by the same electrolyte salt used for the polymer solid electrolyte, 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 organic acid anions Metal salts are preferred, and lithium salts are more preferred.

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

The amount of the polymer such as the copolymer and the electrolyte salt included in the electrode of the present invention is not particularly limited, but is 0.5 to 15 weight of the entire electrode composition (excluding the support). % Range is preferred. 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 may be lowered.
The electrode of the present invention has an excellent charge / discharge cycle, and is suitably used for the polymer solid electrolyte battery of the present invention.

(2) Electrode manufacturing method The electrode manufacturing method of the present invention is characterized in that a solution containing a polymer and an electrolyte salt is cast or coated on a layer containing an electrode active material prepared 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 polymer used as the electrolyte and the polymer used as the electrode may be the same or different in the same element, but are preferably the same.

  The electrolyte salt used is preferably a salt used as an electrolyte, and the salt used as an electrolyte and the electrolyte salt used for an 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.

  In addition to the electrode active material, the layer containing the electrode active material preferably contains at least one selected from polymers used for binders and electrolytes. 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. Examples thereof include resins and rubbers such as styrene butadiene rubber. Among these, a fluororesin (particularly PVDF) is preferable.

  The polymer used as the electrolyte is not particularly limited as long as it is a polymer that is conductive with an electrolyte salt. The polymer used as the battery electrolyte and the polymer used as the electrode may be the same or different in the same element. However, it is preferable that they are the same.

  The layer containing the electrode active material can be produced, for example, by applying a solution containing at least one kind selected from a polymer used for the electrode active material and the binder and the electrolyte on the 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.

As described above, the electrode of the present invention can be produced efficiently and simply.
The electrode of the present invention is suitable as the positive electrode and / or the negative electrode of the polymer solid electrolyte battery of the present invention described above.

  The polymer solid electrolyte battery of the present invention preferably has a carbon-based electrode made of a carbon-based electrode material containing the copolymer. This electrode is suitable as the positive electrode and / or the negative electrode of the polymer solid electrolyte battery of the present invention described above.

The carbon-based electrode contains a carbon-based electrode material as an electrode active material and the copolymer as a binder.
Examples of the carbon-based electrode material include various carbon-based materials obtained by graphite, ketjen black, carbon black, acetylene black, graphite, graphite fluoride, firing, thermal decomposition, CVD (Chemical Vapor Deposition), and the like. .

  The carbon-based electrode can be formed by applying or casting a carbon-based electrode material, a solution or slurry containing the copolymer on a support.

  The amount of the copolymer contained in the carbon-based electrode is not particularly limited, but is preferably in the range of 1 to 15% by weight of the entire electrode composition (excluding the support), and 3 to 10% by weight. The range of is more preferable. If it is less than 1 weight, the effect as a binder cannot fully be exhibited, and if it is 15% by weight or more, it is not preferable as a carbon-based electrode because the conductivity of the electrode itself is lowered.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the scope of the present invention is not limited to an Example.
(Example 1)
<Polymer Solid Electrolyte Containing B-A-B Type Multibranched Polymer Compound in which Block Chain A is Poly-methoxypolyethyleneglycol Monomethacrylate and Block Chain B is Polystyrene>
(1) Synthesis of Block Chain A Under argon atmosphere, 89.40 g of toluene, 0.05 g (0.05 mmol) of dichlorotris (triphenylphosphine) ruthenium, methoxypolyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PME-400) In the formula (XI), m = 9) 22.35 g (45.0 mmol) was added and mixed uniformly, and then 0.03 g (0.2 mmol) of di-n-butylamine and 0.02 g of 2,2-dichloroacetophenone. (0.1 mmol) was added, and the polymerization reaction was started by heating to 80 ° C. with stirring. After 22 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 was 55.0%. 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-PME400-1). The obtained P-PME400-1 was a unimodal polymer having a number average molecular weight (Mn) of 122,500.

(2) Synthesis of B-A-B type multi-branched polymer compound Under an argon atmosphere, 20.37 g of toluene was added to 0.01 g (0.01 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, P-PME400-1 6.13 g (0.05 mmol), styrene 2.60 g (25 mmol), n-octane 0.57 g (5.0 mmol) were added and mixed uniformly, and then di-n-butylamine 0.01 g ( 0.1 mmol) was added and heated to 100 ° C. with stirring to initiate the polymerization reaction. After 22 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 26%. After column purification of the polymerization solution to remove the metal complex and unreacted monomer, toluene was distilled off under reduced pressure, and poly- (styrene-b-PME-400-b-) having methoxypolyethylene glycol as the graft chain was removed. A multi-branched polymer compound having a structure of (styrene) was obtained. This polymer block chain C is the same as the block chain B.

  The obtained multi-branched polymer compound was a unimodal polymer having a ratio of block chain A to block chain B of A / B = 2.06 / 1 (polymerization degree ratio) and Mn = 13,000. Moreover, when the cross section of the film formed by dissolving the obtained multibranched polymer compound in acetone was observed with a transmission electron microscope (TEM), it was found that it had a network type micro phase separation structure.

(3) Production of solid polymer electrolyte membrane and evaluation of physical properties In an argon atmosphere, 1 g of the multi-branched polymer compound obtained by the above operation was dissolved in 25 ml of acetone, and LiClO ₄ 0. After 03 g was added and uniformly dissolved, it was cast on a polytetrafluoroethylene plate, allowed to stand at room temperature for 24 hours, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a uniform solid electrolyte membrane (film thickness) 140 μm). In an argon atmosphere, this film was sandwiched between platinum plates, and ion conductivity was measured by complex impedance analysis using an impedance analyzer (Solartron-1260 type) having a frequency of 5H to 10 MHz. As a result, the ionic conductivity was 4.5 × 10 ⁻⁴ S / cm at 23 ° C.

  Moreover, the cross section of the obtained polymer solid electrolyte was observed with the transmission electron microscope (TEM). The result is shown in FIG. FIG. 1 shows that the membrane structure is a network type microphase separation structure.

<Production of electrode>
(1) 340 mg of LiCoO ₂ powder (manufactured by Nippon Chemical Industry Co., Ltd., Cellseed 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, 170 mg of a 12% by weight N-methylpyrrolidone (NMP) solution of polyvinylidene fluoride (PVdF: Aldrich, molecular weight: 534,000) was added and mixed well with a spatula, and an aluminum foil collection having a thickness of 80 mm × 200 mm × 50 μm A positive electrode layer was prepared by applying a doctor blade having a width of 40 mm and a gap of 50 μm on the electric conductor, 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 produced above was dissolved in tetrahydrofuran (THF: manufactured by Wako Pure Chemical Industries, Ltd., a special grade reagent) and dissolved in a 2 wt% concentration. Anhydrous LiClO ₄ (manufactured by Wako Pure Chemical Industries, Ltd., 0.02 g of a special grade reagent) was dissolved to prepare a solution containing a polymer and an electrolyte salt. 1 ml of this solution was cast on a positive electrode sheet having a coating area of 40 mm × 50 mm prepared in advance, and the solvent was removed under a reduced pressure of 200 torr for 1 hour, so that the polymer and the electrolyte salt were infiltrated into the positive electrode layer. The cast-vacuum drying operation was repeated three times, followed by vacuum drying at 80 ° C. for 3 hours to produce a polymer-containing positive electrode.

<Preparation of polymer solid electrolyte membrane>
On this positive electrode, 1 g of a 20 wt% THF solution of the B-A-B type block graft polymer prepared above and 0.02 g of LiClO ₄ were dissolved in 0.5 g of acetonitrile (AN: Wako Pure Chemical Industries, Ltd., special grade reagent). The liquid mixture was cast, and after forming a microphase separation structure by annealing at 80 ° C. for 2 hours under a nitrogen atmosphere and further for 1 hour at 80 ° C. under vacuum, it was vacuum dried at 120 ° C. for 5 hours, A positive electrode with a solid electrolyte membrane having a thickness of about 40 μm was produced.

<Charge / discharge test>
A Li metal sheet (manufactured by Furuuchi Chemical Co., Ltd., 2000 μm thickness) was attached to the positive electrode with a solid electrolyte membrane, a 2016 coin cell was assembled, and a charge / discharge test was performed. The results are summarized in Table 1.

(Example 2)
In the production of the positive electrode sheet of Example 1, a solid content obtained by dissolving 0.2 g of the polymer prepared in Reference Example 1 and 0.02 g of LiClO ₄ instead of the PVdF / NMP solution was used except that 200 mg of a 10 wt% NMP solution was used. A positive electrode was produced in the same manner as in Example 1. The positive electrode thickness was 30 μm and the content of LiCoO ₂ 4.5 mg / cm ² . Subsequently, in the same manner as in Example 1, a solid electrolyte membrane and a coin cell were produced, and a charge / discharge test was performed. The results are summarized in Table 1.

(Example 3)
The composition of the positive electrode layer was the same as in Example 1 except that 280 mg of LiCoO ₂ , 60 mg of KB, 250 mg of 12% PVdF / NMP solution was used, and 300 mg of the LiClO ₄ added polymer / NMP solution prepared in Example 2 was used. A positive electrode was prepared. The thickness of the positive electrode was 30 μm, and the content of LiCoO ₂ was 48 mg / cm ² . Subsequently, in the same manner as in Example 1, a solid electrolyte membrane and a coin cell were produced, and a charge / discharge test was performed. The results are summarized in Table 1.

Example 4
As a negative electrode active material, 270 mg of natural graphite (Chuetsu Graphite Industries, LF-18A) and 250 mg of 12% PVdF / NMF solution were mixed and kneaded well on a copper foil current collector of 80 mm × 200 mm × 50 μm thickness. The negative electrode sheet was prepared by coating with a doctor blade having a width of 40 mm and a gap of 50 μm, vacuum drying at 100 ° C. for 24 hours, and pressing at ²⁰ Mpa / cm ² . The negative electrode thickness was 40 μm and the content of graphite was 4 mg / cm ² . A cast-drying operation was repeated three times using the polymer solution used in Example 1 for this negative electrode to produce a polymer-containing negative electrode.

  A coin cell was assembled in the same manner as in Example 1 except that this graphite negative electrode was used instead of the Li metal sheet used in Example 1, and a charge / discharge test was performed. The results are summarized in Table 1.

(Examples 5 and 6)
In Examples 2 and 3, a coin cell was assembled using the polymer-containing graphite negative electrode prepared in Example 4 instead of the Li metal sheet, and a charge / discharge test was performed. The results are summarized in Table 1.

<Charging / discharging test method>
(1) Test conditions Voltage range: 3.0 to 4.2 V, current value: 0.2 C, room temperature, 20 cycles (2) measured values Initial discharge capacity, discharge voltage, charge / discharge efficiency, discharge capacity after 20 cycles, Voltage, efficiency

(Example 7) Production of carbon-based electrode As electrode active materials, 10.2 g of natural graphite (manufactured by Chuetsu Graphite Industries Co., Ltd., LF-18A), 10.5 g of MCMB (manufactured by Osaka Gas Chemical Company, MCMB10-10), 12 % PVdF (polyvinylidene fluoride, manufactured by Kureha Chemical Industry Co., Ltd., KF polymer L # 1110) / NMP (N-methylpyrrolidone) solution 18.7 g, and 20% multibranched polymer compound / THF obtained in Example 1 ( Tetrahydrofuran) solution (3.1 g) was mixed and kneaded well, and then applied onto a 50 mm × 500 mm × 50 μm thick copper foil collector with a doctor blade having a width of 40 mm and a gap of 50 μm, and vacuum dried at 100 ° C. for 20 hours. And it pressed at 20 MPa / cm < ² > and produced the electrode sheet.

<Synthesis of C-B-A-B-C type block graft polymer>
Under an argon atmosphere, dichlorotris (triphenylphosphine) ruthenium 0.55 g (0.6 mmol) in 607.3 g of toluene, methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer PME-1000, m in the above formula (XI)) = 23) After adding 203.6 g (189 mmol) and mixing uniformly, 0.29 g (2.2 mmol) of di-n-butylamine and 0.20 g (1.1 mmol) of 2,2-dichloroacetophenone were added and stirred. The polymerization reaction was started by heating to 80 ° C. 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 was 65.0%. Subsequently, column purification of the polymerization solution was performed to remove the metal complex and unreacted monomers, and then toluene was distilled off under reduced pressure to obtain poly-methoxypolyethylene glycol monomethacrylate (hereinafter referred to as “P-PME1000-1”). Abbreviated). The obtained P-PME1000-1 was a unimodal polymer having a number average molecular weight (Mn) of 125,000.

  Under an argon atmosphere, toluene (509.9 g), chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium (0.40 g, 0.49 mmol), “P-PME1000-1” (127.7 g, 1.02 mmol), After 45.1 g (432 mmol) of styrene was added and mixed uniformly, 0.36 g (2.9 mmol) of di-n-butylamine was added and heated to 100 ° C. with stirring to initiate the polymerization reaction. After 22 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 24%. After column purification of the polymerization solution to remove the metal complex and unreacted monomer, toluene was distilled off under reduced pressure, and poly (styrene-b-PME-1000-b-) having methoxypolyethylene glycol as the graft chain was removed. A multi-branched polymer compound having a structure of (styrene) was obtained.

  The obtained multibranched polymer compound was a unimodal polymer in which the ratio of block chain A to block chain B was A / B = 11.5 / 1 (polymerization degree ratio) and Mn = 148,000. Moreover, when the cross section of the film formed by dissolving the obtained multibranched polymer compound in acetone was observed with a transmission electron microscope (TEM), it was found that it had a network type micro phase separation structure.

Under an argon atmosphere, 131.0 g (0.89 mmol) of the multibranched polymer compound, 522.3 g of toluene, 0.45 g (0.58 mmol) of chloropentamethylcyclopentadienylbis (triphenylphosphine) ruthenium, hydroxyethyl 43.9 g (375 mmol) of acrylate (HEA) was added and mixed uniformly, then 0.35 g (2.7 mmol) of di-n-butylamine was added, and the mixture was heated to 80 ° C. with stirring to initiate the polymerization reaction. . After 22 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 was 68.0%. Next, column purification of the polymerization solution was performed to remove metal complexes, unreacted monomers, etc., and then toluene was distilled off under reduced pressure to obtain poly- (HEA-styrene-b-PME-1000-b-styrene-HEA). A block graft polymer having the following structure was obtained.
In the obtained multibranched polymer compound, the ratio of block chain A, block chain B, and block chain C was A / B / C = 11/1 / 2.3 (polymerization degree ratio).

<Preparation of polymer solid electrolyte membrane>
A solution in which 5 g of a 20 wt% dehydrated THF solution of the block graft polymer and 0.08 g of LiClO ₄ were dissolved in 5 g of dehydrated acetone (special grade reagent manufactured by Wako Pure Chemical Industries) was mixed. To this solution was added 0.6 g of a 10% by weight dehydrated THF solution of tolylene 2,4-diisocyanate (TDI: manufactured by Wako Pure Chemical Industries, Ltd.) to adjust the solution to 10% by weight.
2 g of this solution was cast on the carbon-based electrode, the solvent was removed at room temperature in a nitrogen atmosphere, and subsequently heated at 60 ° C. for 1 hour in a nitrogen atmosphere.

<Charge / discharge test>
A carbon-based electrode was used as the positive electrode, a Li metal sheet (manufactured by Furuuchi Chemical Co., 250 μm thickness) was stuck on the polymer solid electrolyte membrane side of the electrode formed by casting, a 2016 coin cell was assembled, and a charge / discharge test was performed. As a result, the initial charge capacity was 338 mAh / g, the initial discharge capacity was 104 mAh / g, and the charge / discharge efficiency was 31%.

  From the above charge / discharge test, it was found that the contact between the active material and the polymer was improved by containing the polymer in the positive electrode, and a practical battery capacity was obtained even in the solid electrolyte battery. Similarly, it was confirmed that a practical battery capacity can be obtained by incorporating a polymer in the graphite negative electrode. It was also confirmed that a good coin cell was formed when a carbon-based electrode was used for the positive electrode.

1 is a transmission electron micrograph of a cross section of an electrolyte membrane containing a B-A-B type multibranched polymer compound obtained in Example 1. FIG.

Claims (51)

Formula (I)

(Wherein R _{1 to} R ₃ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁ and R ₃ may be bonded to form a ring, and R _4a and R _4b are 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 2 to 100, and R _4a and R _4b represent , Which may be the same or different from each other), and a block chain A having a repeating unit represented by formula (II):

(Wherein R _{6 to} R ₈ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₉ represents an aryl group) and a block chain B having a repeating unit represented by A polymer solid electrolyte battery comprising a polymer solid electrolyte in which a chain C contains a copolymer in which B, A, and C are arranged in this order, and an electrolyte salt. The block chain C 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). The polymer solid electrolyte battery according to claim 1, wherein   3. The polymer solid electrolyte battery according to claim 1, wherein the copolymer is a copolymer in which the block chains A to C are combined with B-A-C. .   The polymer solid electrolyte battery according to any one of claims 1 to 3, wherein a degree of polymerization of the repeating unit represented by the formula (I) is 10 or more.   The polymer solid electrolyte battery according to any one of claims 1 to 4, wherein the degree of polymerization of the repeating unit represented by the formula (II) is 5 or more.   The polymer solid electrolyte battery according to any one of claims 2 to 5, wherein the degree of polymerization of the repeating unit represented by the formula (III) is 5 or more.   In the said formula (I), m is an integer in any one of 5-100, The polymer solid electrolyte battery in any one of Claims 1-6 characterized by the above-mentioned.   In the said formula (I), m is an integer in any one of 10-100, The polymer solid electrolyte battery in any one of Claims 1-7 characterized by the above-mentioned. The polymer solid electrolyte battery according to claim 2, wherein R ₁₃ in the formula (III) is an aryl group.   Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit contained in the block chain C [repeating represented by the formula (I) Unit / (repeat unit represented by formula (II) + repeat unit contained in block chain C)] is in the range of 1/30 to 30/1. The solid polymer electrolyte battery described in 1.   Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) [represented by the formula (I) The repeating unit / (repeating unit represented by formula (II) + repeating unit represented by formula (III))] is in the range of 1/30 to 30/1. The polymer solid electrolyte battery according to any one of 10.   The polymer solid electrolyte battery according to claim 1, wherein the copolymer has a number average molecular weight in the range of 5,000 to 1,000,000.   The polymer solid electrolyte battery according to claim 1, wherein the copolymer has a microphase separation structure.   The polymer solid electrolyte battery according to claim 1, wherein the polymer solid electrolyte has a microphase separation structure.   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 solid polymer electrolyte battery described in 1.   The polymer electrolyte electrolyte according to claim 1, wherein the electrolyte salt is a lithium salt.   The polymer solid electrolyte battery according to any one of claims 1 to 16, wherein the polymer solid electrolyte contains 90% by weight or more of the copolymer.   The polymer solid electrolyte battery according to claim 1, comprising a carbon-based electrode made of a carbon-based electrode material containing the copolymer.   The polymer solid according to claim 1, comprising a carbon-based electrode made of a carbon-based electrode material containing the copolymer in an amount of 1 to 15% by weight as a positive electrode or a negative electrode. Electrolyte battery.   The polymer solid electrolyte battery according to claim 1, wherein the polymer solid electrolyte is an ion conductive membrane having a network type microphase separation structure. Electrode active material, electrolyte salt, and formula (I)

(Wherein R _{1 to} R ₃ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, R ₁ and R ₃ may be bonded to form a ring, and R _4a and R _4b are 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 2 to 100, and R _4a and R _4b represent , Which may be the same or different, each having a repeating unit represented by formula (II)

(Wherein R _{6 to} R ₈ each independently represents a hydrogen atom or a C1 to C10 hydrocarbon group, and R ₉ represents an aryl group) and a block chain B having a repeating unit represented by An electrode, wherein the chain C includes a copolymer in which B, A, and C are arranged in this order. The block chain C 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). The electrode according to claim 21, characterized in that   The electrode according to claim 21 or 22, wherein the copolymer is a copolymer in which the block chains A to C are combined with B-A-C.   24. The electrode according to claim 21, wherein the degree of polymerization of the repeating unit represented by the formula (I) is 10 or more.   The electrode according to any one of claims 21 to 24, wherein the degree of polymerization of the repeating unit represented by the formula (II) is 5 or more.   The electrode according to any one of claims 22 to 25, wherein the degree of polymerization of the repeating unit represented by the formula (III) is 5 or more.   27. The electrode according to any one of claims 21 to 26, wherein m is an integer of 5 to 100 in the formula (I).   27. The electrode according to any one of claims 21 to 26, wherein in the formula (I), m is an integer of 10 to 100. The electrode according to any one of claims 22 to 28, wherein R ₁₃ in the formula (III) is an aryl group.   Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit contained in the block chain C [repeating represented by the formula (I) 30. The unit / (repeating unit represented by formula (II) + repeating unit contained in block chain C)] is in the range of 1/30 to 30/1. Electrode.   Molar ratio of the repeating unit represented by the formula (I) and the sum of the repeating unit represented by the formula (II) and the repeating unit represented by the formula (III) [represented by the formula (I) The repeating unit / (repeating unit represented by formula (II) + repeating unit represented by formula (III))] is in the range of 1/30 to 30/1. 30. The electrode according to any one of 30.   The electrode according to any one of claims 21 to 31, wherein the copolymer has a number average molecular weight in the range of 5,000 to 1,000,000.   The electrode according to claim 21, wherein the copolymer has a microphase separation structure.   The electrode according to any one of claims 21 to 33, wherein the copolymer and the electrolyte salt are combined in a range of 0.5 to 15% by weight.   The electrode according to any one of claims 21 to 34, which is a positive electrode and further contains a conductive material.   36. A polymer solid electrolyte battery, wherein the positive electrode is the electrode according to claim 35, and the negative electrode is made of the electrode according to any of claims 21 to 34 or an alkali metal.   The polymer solid electrolyte battery according to claim 36, which is the polymer solid electrolyte battery according to claim 1.   A method for producing an electrode, comprising casting or coating a solution containing a polymer and an electrolyte salt on a layer containing an electrode active material prepared on a support.   The method for producing an electrode according to claim 38, wherein a solution containing a polymer and an alkali metal salt is cast or applied a plurality of times.   40. The method for producing an electrode according to claim 38 or 39, wherein the layer containing the electrode active material contains at least one selected from an electrode active material and a polymer used as a binder and an electrolyte.   The method for manufacturing an electrode according to any one of claims 38 to 40, wherein the layer containing the electrode active material contains a conductive material.   The layer containing the electrode active material is a layer obtained 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 solution. The method for producing an electrode according to any one of claims 38 to 41, wherein:   The method for producing an electrode according to any one of claims 38 to 42, wherein the polymer is used as an electrolyte.   44. The method for producing an electrode according to claim 39, wherein a solid content concentration in the solution containing the polymer and the alkali metal salt is 0.5 to 10% by weight.   The electrode manufacturing method according to any one of claims 38 to 44, wherein the electrode according to any one of claims 21 to 35 is manufactured.   A solution containing a polymer and an electrolyte salt is further cast or applied on the electrode obtained by the method according to any one of claims 38 to 45 to form an electrolyte layer, and another electrode is provided. A method for producing a polymer solid electrolyte battery.   47. The method for producing a polymer solid electrolyte battery according to claim 46, wherein a polar solvent is used as a solvent of the solution containing the polymer and the electrolyte salt, and the solution is heat-treated.   48. The method for producing a solid polymer electrolyte battery according to claim 46, wherein a solid content concentration in the solution containing the polymer and the electrolyte salt is in the range of 0.5 to 30% by weight.   The method for producing a polymer solid electrolyte battery according to any one of claims 46 to 48, wherein the polymer solid electrolyte battery according to any one of claims 1 to 20 is produced.   A method for producing a solid electrolyte by casting or coating a solution containing a polymer and an electrolyte salt on a support, comprising a step of heat-treating a polar solvent as a solvent and containing the solvent. Manufacturing method.   51. The method for producing a solid electrolyte according to claim 50, wherein the solid content concentration in the solution containing the polymer and the electrolyte salt is in the range of 0.5 to 30% by weight.

Images