Electricity storage device binder aqueous solution, electricity storage device slurry, electricity storage device electrode, electricity storage device separator, electricity storage device separator / electrode laminate, and electricity storage device

Abstract

An aqueous binder solution for electricity storage devices, the aqueous binder solution for electricity storage devices comprising a polyamic acid and water, the polyamic acid comprising an aliphatic diamine unit, and the polyamic acid being an amine salt.

Description

Technical Field

[0001] The present disclosure relates to an aqueous solution of an electric storage device binder, an electric storage device slurry, an electric storage device electrode, an electric storage device separator, an electric storage device separator / electrode laminate, and an electric storage device. Background Art

[0002] The present applicant is developing an electrical storage device binder containing poly(meth)acrylamide.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-006333 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] An object of the present invention is to provide an aqueous solution of a storage device binder having excellent bonding properties and coating properties.

[0008] Technical means to solve the problem

[0009] The following items are provided in accordance with the present disclosure.

[0010] (Item 1)

[0011] An aqueous solution of an adhesive for an electrical storage device,

[0012] The electrical storage device binder aqueous solution comprises polyamic acid and water,

[0013] The polyamic acid comprises an aliphatic diamine unit,

[0014] The polyamic acid is an amine salt.

[0015] (Item 2)

[0016] The aqueous solution of the electrical storage device binder according to the above item, wherein the polyamic acid contains a polyamine unit.

[0017] (Item 3)

[0018] A slurry for an electrical storage device,

[0019] The electrical storage device slurry comprises polyamic acid, water, and electrode active materials or non-conductive particles.

[0020] The polyamic acid comprises an aliphatic diamine unit,

[0021] The polyamic acid is an amine salt.

[0022] (Item 4)

[0023] An electric storage device electrode comprising a dried product of the electric storage device slurry according to the above item on a current collector.

[0024] (Item 5)

[0025] An electric storage device separator comprising a dried product of the electric storage device slurry according to the above item on a substrate.

[0026] (Item 6)

[0027] An electric storage device separator / electrode laminate having a dried product of the electric storage device slurry according to the above item on the active material side of an electrode.

[0028] (Item 7)

[0029] An electric storage device comprising one or more selected from the group consisting of the electric storage device electrode according to the above item, the electric storage device separator according to the above item, and the electric storage device separator / electrode laminate according to the above item.

[0030] (Project A1)

[0031] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mass % content (the diamine unit / the polyamic acid) is 10% by mass to 70% by mass.

[0032] (Item A2)

[0033] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mass % content (the diamine unit / the polyamic acid) is 15% by mass to 45% by mass.

[0034] (Item A3)

[0035] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mol% content (the diamine unit / the polyamic acid) is 45 mol% to 56 mol%.

[0036] (Item A4)

[0037] In the electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, the aliphatic diamine unit is one or more selected from the group consisting of diaminoalkylene units and diaminocycloalkylene units.

[0038] (Item A5)

[0039] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the aliphatic diamine unit is a 1,3-bisaminomethylcyclohexane unit.

[0040] (Item A6)

[0041] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mass % content (the aliphatic diamine unit / the polyamic acid) is 1% by mass to 55% by mass.

[0042] (Item A7)

[0043] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mol% content (the aliphatic diamine unit / the polyamic acid) is 2 mol% to 56 mol%.

[0044] (Item A8)

[0045] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the tetracarboxylic dianhydride is one or more selected from the group consisting of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

[0046] (Item A9)

[0047] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the polyamine is a diaminodialkylamine.

[0048] (Item A10)

[0049] In the electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, the polyamine is diaminodipropylamine.

[0050] (Item A11)

[0051] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mass % content (polyamine unit / polyamic acid) is 0% by mass to 57% by mass.

[0052] (Item A12)

[0053] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the mol% content (polyamine unit / polyamic acid) is 0 mol% to 56 mol%.

[0054] (Item A13)

[0055] In the electrical storage device binder aqueous solution or the electrical storage device slurry according to any one of the above items, the amine salt is at least one selected from the group consisting of trialkylamine salts, alkanolamine salts, imidazole salts, and diamine salts.

[0056] (Item A14)

[0057] The electrical storage device binder aqueous solution according to any one of the above items or the electrical storage device slurry according to any one of the above items, wherein the boiling point (amine) is 120°C to 175°C.

[0058] One or more of the features mentioned may also be provided in combinations other than the combinations explicitly stated.

[0059] Effects of the Invention

[0060] The electrical storage device binder aqueous solution of the present invention exhibits good bonding properties and coating properties. DETAILED DESCRIPTION

[0061] Throughout the present disclosure, the ranges of the values ​​of various physical property values, contents, etc. can be set as appropriate (for example, selected from the values ​​described in the following items). Specifically, regarding the value α, when A3, A2, A1 (assuming A3>A2>A1) and the like are listed, the range of the value α is listed as follows: A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, and the like.

[0062] As long as the problems to be solved by the present invention are solved, the components, conditions, numerical values, etc. are not particularly limited.

[0063] "αβ amount (A / B)" refers to the β amount (α) of A relative to 100α of B. Examples of α include mass %, mole %, and parts by mass. Examples of β amount include content and usage amount. "Mass % content (A / B)" refers to the content (mass %) of A relative to 100% of B.

[0064] "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.

[0065] The "non-volatile component" refers to the total mass of components other than the organic solvent and water. In one embodiment, the "non-volatile component of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C to a constant weight.

[0066] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

[0067] Examples of the straight-chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0068] The "branched alkyl group" refers to a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group and the group does not have a cyclic structure.

[0069] Examples of the branched alkyl group include isopropyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0070] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, a condensed cycloalkyl group, etc. Furthermore, a cycloalkyl group in which at least one hydrogen atom is substituted by an alkyl group is also considered to be a cycloalkyl group.

[0071] "Monocyclic ring" refers to a ring structure formed by covalent bonds of carbon atoms and having no internal bridging structure. "Fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., they share (fuse) only one side of each ring). "Cross-linked ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0072] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0073] Examples of the cross-linked cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0074] Furthermore, the alkyl group also includes a combination of a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of such a combination include a cycloalkylalkyl group and the like.

[0075] The cycloalkylalkyl group is represented by the following formula.

[0076] R calkyl -R alkyl -

[0077] (Where R calkyl Represents a cycloalkyl group. alkyl represents an alkyl group.)

[0078] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0079] Examples of the linear alkylene group include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decamethylene.

[0080] Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

[0081] Examples of the cycloalkylene group include monocyclic cycloalkylene groups, cross-linked cycloalkylene groups, and condensed cycloalkylene groups. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0082] Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0083] Examples of the cross-linked cycloalkylene group include tricyclodecanylene, adamantylene, and norbornylene.

[0084] Examples of the fused ring cycloalkylene group include biscyclodecylene and the like.

[0085] Furthermore, the alkylene group also includes a combination of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of such a combination include cycloalkylenealkylene groups and alkylenecycloalkylenealkylene groups.

[0086] The cycloalkylenealkylene group is represented by the following formula.

[0087] -R calkylene -R alkylene -

[0088] (Where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0089] The alkylenecycloalkylenealkylene group is represented by the following formula.

[0090] -R alkylene -R calkylene -R alkylene -

[0091] (Where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0092] The aromatic group (aryl group, arylene group) may be substituted or unsubstituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, and a carbonylaryl group.

[0093] Examples of the aryl group include a monocyclic aryl group and a condensed ring aryl group.

[0094] Examples of the monocyclic aryl group include phenyl, tolyl, and mesityl.

[0095] Examples of the fused ring aryl group include naphthyl and the like.

[0096] Examples of the arylene group include a monocyclic arylene group and a condensed ring arylene group.

[0097] Examples of the monocyclic arylene group include a phenylene group and a tolylene group.

[0098] Examples of the fused ring arylene group include naphthylene and the like.

[0099] [Electricity storage device binder aqueous solution]

[0100] The present disclosure relates to an aqueous solution of an electrical storage device binder.

[0101] The electrical storage device binder aqueous solution comprises polyamic acid and water,

[0102] The polyamic acid comprises an aliphatic diamine unit,

[0103] The polyamic acid is an amine salt.

[0104] <Polyamic acid>

[0105] The polyamic acid can be used alone or in combination of two or more.

[0106] (Diamine unit)

[0107] The diamines may be used alone or in combination of two or more.

[0108] Examples of the mass % content (diamine unit / polyamic acid) include 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, and 10 mass %. In one embodiment, the content is preferably 10 to 70 mass %.

[0109] Examples of the mol% content (diamine unit / polyamic acid) include 56 mol%, 55 mol%, 53 mol%, 51 mol%, 50 mol%, 49 mol%, 47 mol%, and 45 mol%. In one embodiment, the content is preferably 45 to 56 mol%.

[0110] Aliphatic diamines

[0111] The "aliphatic diamine" refers to a diamine in which the portion excluding two amino groups (-NH2) is an aliphatic group.

[0112] Examples of the aliphatic group include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, and an alkynylene group.

[0113] Examples of the aliphatic diamine include diaminoalkylene and diaminocycloalkylene. In one embodiment, the carbon number (aliphatic diamine) is preferably 2 to 9, more preferably 3 to 9. The reason for this preference is, for example, to prevent turbidity.

[0114] Examples of the diaminoalkylene group include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

[0115] Examples of the diaminocycloalkylene group include diaminocyclohexane, diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, dimethyl-diaminodicyclohexylmethane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ] decane, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, etc.

[0116] Examples of the mass % content (aliphatic diamine unit / polyamic acid) include 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and 1 mass %. In one embodiment, the content is preferably 1 to 55 mass %.

[0117] Examples of the mol% content (aliphatic diamine unit / polyamic acid) include 56 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 2 mol%. In one embodiment, the content is preferably 2 mol% to 56 mol%.

[0118] ·Diamines other than aliphatic diamines: other diamines

[0119] In one embodiment, the polyamic acid may optionally contain other diamine units. Other diamines may be used alone or in combination of two or more.

[0120] Other diamines include, for example, diaminopolysiloxane, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminobis-trifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, aminophenoxyphenyl sulfide, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, Benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane, bis(aminoalkyl)ether, bis(aminoalkoxyalkyl)ether, bis(aminoalkoxy)alkane, bis[(aminoalkoxy)alkoxy]alkane, (poly)ethylene glycol bis(aminoalkyl)ether, bis(aminoaryloxy)pyridine, etc.

[0121] Examples of diaminopolysiloxane include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 1,3-bis(4-aminobutyl)tetramethyldisiloxane.

[0122] Examples of the bisaminophenoxyphenylpropane include 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0123] Examples of diaminodiphenyl ether include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether.

[0124] Examples of phenylenediamine include p-phenylenediamine, m-phenylenediamine, and the like.

[0125] Examples of diaminodiphenyl sulfide include 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, and 4,4′-diaminodiphenyl sulfide.

[0126] Examples of diaminodiphenyl sulfone include 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfone.

[0127] Examples of the diaminobenzophenone include 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, and 3,4'-diaminobenzophenone.

[0128] Examples of diaminodiphenylmethane include 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-diaminodiphenylmethane.

[0129] Examples of diaminophenylpropane include 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, and 2-(3-aminophenyl)-2-(4-aminophenyl)propane.

[0130] Examples of the diaminophenylhexafluoropropane include 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, and 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane.

[0131] Examples of the diaminophenylphenylethane include 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, and 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane.

[0132] Examples of the bisaminophenoxybenzene include 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene.

[0133] Examples of the bisaminobenzoylbenzene include 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, and 1,4-bis(4-aminobenzoyl)benzene.

[0134] Examples of bisaminodimethylbenzylbenzene include 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, and 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene.

[0135] Examples of bisaminobis-trifluoromethylbenzylbenzene include 1,3-bis(3-amino-α,α-bis-trifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-bis-trifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-bis-trifluoromethylbenzyl)benzene, and 1,4-bis(4-amino-α,α-bis-trifluoromethylbenzyl)benzene.

[0136] Examples of the aminophenoxybiphenyl include 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, and 4,4'-bis(4-aminophenoxy)biphenyl.

[0137] Examples of the aminophenoxyphenyl ketone include bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone.

[0138] Examples of aminophenoxyphenyl sulfide include bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide.

[0139] Examples of aminophenoxyphenyl sulfone include bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone.

[0140] Examples of the aminophenoxyphenyl ether include bis[4-(3-aminophenoxy)phenyl]ether and bis[4-(4-aminophenoxy)phenyl]ether.

[0141] Examples of the aminophenoxyphenylpropane include 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

[0142] Examples of bis(aminophenoxybenzoyl)benzene include 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, and 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene.

[0143] Examples of bis(aminophenoxy-α,α-dimethylbenzyl)benzene include 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, and 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene.

[0144] Examples of bis[(aminoaryloxy)benzoyl]diphenyl ether include 4,4′-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether.

[0145] Examples of the bis(amino-α,α-dimethylbenzylphenoxy)benzophenone include 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone.

[0146] Examples of bis[amino-α,α-dimethylbenzylphenoxy]diphenylsulfone include 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone.

[0147] Examples of 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone include 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone.

[0148] Examples of the diaminodiaryloxybenzophenone include 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3'-diamino-4,4'-diphenyloxybenzophenone.

[0149] Examples of the diaminoaryloxybenzophenone include 3,3′-diamino-4-phenoxybenzophenone and 3,3′-diamino-4-biphenyloxybenzophenone.

[0150] Examples of the 6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane include 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane and 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane.

[0151] Examples of the bis(aminoalkyl)ether include bis(aminomethyl)ether, bis(2-aminoethyl)ether, and bis(3-aminopropyl)ether.

[0152] Examples of the bis(aminoalkoxyalkyl)ether include bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminopropoxy)ethyl]ether.

[0153] Examples of the bis(aminoalkoxy)alkane include 1,2-bis(aminomethoxy)ethane and 1,2-bis(2-aminoethoxy)ethane.

[0154] Examples of the bis[(aminoalkoxy)alkoxy]alkane include 1,2-bis[2-(aminomethoxy)ethoxy]ethane and 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane.

[0155] Examples of the (poly)ethylene glycol bis(aminoalkyl) ether include ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, and triethylene glycol bis(3-aminopropyl) ether.

[0156] Examples of the bis(aminoaryloxy)pyridine include 2,6-bis(3-aminophenoxy)pyridine.

[0157] Examples of the mass % content (other diamine units / polyamic acid) include 56 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 56 mass %.

[0158] Examples of the mol% content (other diamine units / polyamic acid) include 53 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 1 mol%, and 0 mol%. In one embodiment, the content is preferably 0 to 53 mol%.

[0159] (Tetracarboxylic anhydride unit)

[0160] The tetracarboxylic anhydrides may be used alone or in combination of two or more.

[0161] Examples of tetracarboxylic anhydrides include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,3,4-benzene tetracarboxylic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy) ] diphthalic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis(2 ,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(2,3-dicarboxyphenoxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3, 6,7-Anthracenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, and the like.

[0162] In one embodiment, as the tetracarboxylic anhydride, preferably, a compound represented by the following formula is used.

[0163] [Chemistry 1]

[0164]

[0165] (Wherein, X represents a single bond, -SO2-, -CO-, -O-, -O-C6H4-C(CH3)2-C6H4-O-, -C(CH3)2-, -O-C6H4-SO2-C6H4-O-, -C(CHF2)2-, -C(CF3)2-, -COO-(CH2) p -OCO- or -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO-. p represents an integer from 1 to 20.)

[0166] The mass % content (tetracarboxylic anhydride unit / polyamic acid) is, for example, 89 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 34 mass %, etc. In one embodiment, the content is preferably 34 mass % to 89 mass %.

[0167] Examples of the mol% content (tetracarboxylic anhydride unit / polyamic acid) include 55 mol%, 53 mol%, 51 mol%, 50 mol%, 49 mol%, 47 mol%, 45 mol%, and 44 mol%. In one embodiment, the content is preferably 44 to 55 mol%.

[0168] (Polyamine unit)

[0169] In one embodiment, the polyamic acid may optionally contain a polyamine unit. The polyamine may be used alone or in combination of two or more.

[0170] "Polyamine" refers to an amine having three or more amino groups.

[0171] In one embodiment, the polyamine is preferably a triamine, more preferably a diaminodialkylamine.

[0172] In one embodiment, the diaminodialkylamine is represented by the following formula.

[0173] H2N-R dd1 -NH-R dd2 -NH2

[0174] (Where R dd1 、R dd2 R represents an alkylene group. dd1 、R dd2 are the same or different radicals.)

[0175] Examples of the diaminodialkylamine include diaminodiethylamine, diaminodipropylamine, diaminodibutylamine, diaminodipentylamine, diaminodihexylamine, and spermidine.

[0176] Examples of polyamines other than those mentioned above include triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethyleneheptamine, pentaethyleneheptamine, and spermine.

[0177] Examples of the mass % content (polyamine unit / polyamic acid) include 57 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 to 57 mass %.

[0178] Examples of the mol% content (polyamine unit / polyamic acid) include 56 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 1 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 56 mol%.

[0179] (A unit that is not any of the above: other units)

[0180] The polyamic acid may optionally contain monomer units other than any of the above monomers (other monomers). Other monomers may be used alone or in combination of two or more.

[0181] Examples of other monomers include tricarboxylic acid anhydride units and dicarboxylic acid anhydride units.

[0182] Examples of the mass % content (other monomer units / polyamic acid) include less than 10 mass %, less than 9 mass %, less than 7 mass %, less than 5 mass %, less than 4 mass %, less than 2 mass %, less than 1 mass %, less than 0.9 mass %, less than 0.7 mass %, less than 0.5 mass %, less than 0.4 mass %, less than 0.2 mass %, less than 0.1 mass %, and 0 mass %. In one embodiment, the content is preferably less than 10 mass %, more preferably less than 5 mass %, further preferably less than 1 mass %, and particularly preferably 0 mass %.

[0183] The mol% content (other monomer units / polyamic acid) is, for example, less than 10 mol%, less than 9 mol%, less than 7 mol%, less than 5 mol%, less than 4 mol%, less than 3 mol%, less than 2 mol%, less than 1 mol%, or 0 mol%. In one embodiment, the content is preferably less than 10 mol%, more preferably less than 5 mol%, further preferably less than 1 mol%, and particularly preferably 0 mol%.

[0184] (Amine salt)

[0185] The amines may be used alone or in combination of two or more.

[0186] Examples of the amine salt include trialkylamine salts, alkanolamine salts, imidazole salts, and diamine salts.

[0187] Examples of the trialkylamine salt include trimethylamine salt, triethylamine salt, tripropylamine salt, tributylamine salt, and dimethylcyclohexylamine salt.

[0188] Examples of the alkanolamine salt include ethanolamine salt, diethanolamine salt, and triethanolamine salt.

[0189] Examples of the ethanolamine salt include ethanol dimethylamine salt, ethanol diethylamine salt, ethanol dipropylamine salt, and ethanol dibutylamine salt.

[0190] Examples of the imidazolium salt include imidazolium salt and dimethylimidazolium salt.

[0191] Examples of the diamine salt include tetramethylethylenediamine salt, tetramethylpropylenediamine salt, and tetramethylbutylenediamine salt.

[0192] Examples of the boiling point (amine) include 175° C., 170° C., 165° C., 160° C., 155° C., 150° C., 145° C., 140° C., 135° C., 130° C., 125° C., and 120° C. In one embodiment, the boiling point is preferably 120° C. to 175° C. This is preferably because, for example, the thermal decomposition temperature of the cured adhesive is increased.

[0193] In one embodiment, the amine salt is preferably an acyclic amine salt. "Acyclic amine" refers to an amine in which nitrogen is not a ring atom. For example, dimethylcyclohexylamine is an acyclic amine.

[0194] In one embodiment, the mole % content (carboxyl group (-COOH) of amine / polyamic acid) is, for example, 200 mol%, 175 mol%, 150 mol%, 125 mol%, 100 mol%, 75 mol%, 50 mol%, 30 mol%, etc. In one embodiment, the content is preferably 30 mol% to 200 mol%, more preferably 50 mol% to 150 mol%, and even more preferably 100 mol% to 150 mol%.

[0195] <Production Method (Polyamic Acid)>

[0196] The production of polyamic acid can be carried out by heating a compound group containing an aliphatic diamine, a tetracarboxylic anhydride, and, if necessary, other diamines, diaminodialkylamines, and other monomers in water. The amine salt can be added at least one of before, during, or after the production of the polyamic acid.

[0197] In one embodiment, the reaction temperature is preferably 20°C to 90°C.

[0198] In one embodiment, the reaction time is preferably 0.01 to 10 hours.

[0199] <Physical properties (polyamic acid), etc.>

[0200] Examples of the number average molecular weight (polyamic acid: Mn) include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000, 90,000, 70,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, and 2,000. In one embodiment, the number average molecular weight is preferably 2,000 to 500,000.

[0201] Examples of measurement conditions (number average molecular weight) include the following conditions.

[0202] · Measurement equipment: Gel Permeation Chromatograph (GPC) (Model: HLC-8220) manufactured by Tosoh Co., Ltd.

[0203] Column: TSK gel guard column (gel guardcolumn) PW XL 、TSK-GELG4000、TSK-GELα-M (all manufactured by Tosoh Co., Ltd.)

[0204] Eluent: 0.2M NaNO3 50mM phosphate buffer / acetonitrile = 90 / 10 (v / v) aqueous solution

[0205] Column temperature: 40°C

[0206] Calibration curve: Standard polyethylene oxide-polyethylene glycol

[0207] · Measurement method: The polyamic acid aqueous solution was dissolved in an eluent so as to have a concentration of 0.10% by mass, and the mixture was filtered before measurement.

[0208] Examples of the B-type viscosity (electrical storage device binder aqueous solution) include 20,000 mPa·s, 17,500 mPa·s, 15,000 mPa·s, 12,500 mPa·s, 10,000 mPa·s, 9,000 mPa·s, 7,500 mPa·s, 5,000 mPa·s, 4,500 mPa·s, 4,000 mPa·s, 3,500 mPa·s, 3,000 mPa·s, 2,500 mPa·s, 2,000 mPa·s, 1,500 mPa·s, 1,000 mPa·s, 500 mPa·s, 200 mPa·s, 100 mPa·s, 50 mPa·s, and 10 mPa·s. In one embodiment, the B-type viscosity is preferably 10 to 20,000 mPa·s.

[0209] The measurement conditions (B-type viscosity) are as follows.

[0210] Solid content concentration: 15% by mass

[0211] Measurement temperature: 25°C

[0212] B-type viscometer: manufactured by Toki Industry Co., Ltd., product name: "B-type viscometer TVB-10"

[0213] Viscosity 10mPa·s to 10,000mPa·s: No. 3 rotor, 12rpm

[0214] Viscosity 10,000 mPa·s and above 20,000 mPa·s: No. 3 rotor, 6 rpm

[0215] Viscosity 20,000 mPa·s and above 100,000 mPa·s: No. 4 rotor, 6 rpm

[0216] Examples of the glass transition temperature (polyamic acid) include 350° C., 325° C., 300° C., 275° C., 250° C., 225° C., 200° C., and 180° C. In one embodiment, the glass transition temperature (polyamic acid) is preferably 180° C. or higher, more preferably 180° C. to 350° C.

[0217] The glass transition temperature can be measured by differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), and the like.

[0218] The measurement conditions (glass transition temperature) are as follows.

[0219] Temperature range: -100℃~300℃

[0220] Heating rate: 10℃ / min

[0221] Examples of the mass % content (polyamic acid / electrical storage device binder aqueous solution) include 25 mass %, 20 mass %, 19 mass %, 15 mass %, 14 mass %, 12 mass %, 10 mass %, 9 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, and 1 mass %. In one embodiment, the content is preferably 1 to 25 mass %.

[0222] Water

[0223] Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.

[0224] Examples of the mass % content (water / electricity storage device binder aqueous solution) include 99 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, and 75 mass %. In one embodiment, the content is preferably 75 mass % to 99 mass %.

[0225] Examples of the mass ratio (polyamic acid / water) include 0.33, 0.30, 0.25, 0.24, 0.22, 0.20, 0.18, 0.15, 0.12, 0.10, 0.09, 0.07, and 0.05. In one embodiment, the mass ratio is preferably 0.05 to 0.33.

[0226] <Other adhesives>

[0227] In one embodiment, the electrical storage device binder aqueous solution may optionally contain a binder other than polyamic acid (another binder). The other binders may be used alone or in combination of two or more.

[0228] Examples of other binders include diene copolymers, fluorine copolymers, and copolymers other than those mentioned above.

[0229] Examples of the diene copolymer include styrene-butadiene copolymers, polybutadiene polymers, acrylonitrile-butadiene copolymers, methyl methacrylate-butadiene copolymers, and carboxyl-modified styrene-butadiene copolymers.

[0230] Examples of fluorine-based copolymers include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxy alkane (PFA)), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0231] Examples of copolymers other than those mentioned above include polyurethane polymers, poly(meth)acrylate polymers, vinyl chloride polymers, vinyl acetate polymers, vinyl acetate-ethylene copolymers, polyethylene, polypropylene, polyethylene terephthalate, polystyrene polymers, and poly(meth)acrylamide.

[0232] The content (other binders / polyamic acid) in parts by mass includes, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, and 0 parts by mass. In one embodiment, the content is preferably 0 to 100 parts by mass.

[0233] <Dispersion (emulsion)>

[0234] In one embodiment, the aqueous solution of the electrical storage device binder may optionally contain a dispersion (emulsion). The dispersions (emulsions) may be used alone or in combination of two or more.

[0235] Examples of dispersions (emulsions) include styrene-butadiene copolymer latex, polystyrene polymer latex, polybutadiene polymer latex, acrylonitrile-butadiene copolymer latex, polyurethane polymer latex, polymethyl methacrylate polymer latex, methyl methacrylate-butadiene copolymer latex, polyacrylate polymer latex, vinyl chloride polymer latex, vinyl acetate polymer latex, vinyl acetate-ethylene copolymer latex, polyethylene emulsion, carboxyl-modified styrene-butadiene copolymer resin emulsion, acrylic resin emulsion, polyethylene, polypropylene, polyethylene terephthalate, alginic acid and / or its salts, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0236] The content in parts by mass (dispersion (emulsion) / polyamic acid) is, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, 0 parts by mass, etc. In one embodiment, the content is preferably 0 to 100 parts by mass.

[0237] Thickener

[0238] In one embodiment, the aqueous solution of the electrical storage device binder may optionally contain a thickener. Thickeners may be used alone or in combination of two or more.

[0239] Examples of the thickener include cellulose polymers and / or salts thereof, polyvinyl alcohols, (modified) poly(meth)acrylic acid and / or salts thereof, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, oxidized starch, starch phosphate, casein, modified starch, hydrogenated acrylonitrile-butadiene copolymer, and the like.

[0240] Examples of the cellulose polymer and / or its salt include carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose.

[0241] Examples of the polyvinyl alcohols include copolymers of (anhydrous) maleic acid and / or fumaric acid and vinyl alcohol.

[0242] The content (thickener / polyamic acid) in parts by mass includes, for example, 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 19 parts by mass, 17 parts by mass, 15 parts by mass, 13 parts by mass, 10 parts by mass, 9 parts by mass, 7 parts by mass, 5 parts by mass, 4 parts by mass, 2 parts by mass, 1 part by mass, and 0 parts by mass. In one embodiment, the content is preferably 0 to 100 parts by mass.

[0243] <Additives>

[0244] The aqueous solution of the electrical storage device binder may optionally contain any of the above-mentioned additives. The additives may be used alone or in combination of two or more.

[0245] Examples of the additives include dispersants, leveling agents, antioxidants, and organic solvents.

[0246] Examples of the dispersant include anionic dispersants, cationic dispersants, nonionic dispersants, and polymer dispersants.

[0247] Examples of the leveling agent include surfactants.

[0248] Examples of the surfactant include alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.

[0249] Examples of the antioxidant include phenol compounds, hydroquinone compounds, organic phosphine compounds, sulfur compounds, phenylenediamine compounds, and polymer-type phenol compounds.

[0250] The "polymer type phenol compound" refers to a polymer having a phenol structure. The weight average molecular weight (polymer type phenol compound) is preferably 200 to 1000, more preferably 600 to 700.

[0251] Examples of organic solvents include aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, lower alcohol solvents, ketone solvents, acetate solvents, urea solvents, alkoxy-containing amide solvents, ester-containing amide solvents, etc. In one embodiment, the mass % (total amount of urea solvents, alkoxy-containing amide solvents, and ester-containing amide solvents / solvent) is, for example, less than 5 mass %, less than 2 mass %, less than 1 mass %, or 0 mass %.

[0252] Examples of the content (additive / polyamic acid) include less than 5 parts by mass, less than 4 parts by mass, less than 2 parts by mass, less than 1 part by mass, less than 0.9 parts by mass, less than 0.5 parts by mass, less than 0.4 parts by mass, less than 0.2 parts by mass, less than 0.1 parts by mass, less than 0.09 parts by mass, less than 0.05 parts by mass, less than 0.04 parts by mass, less than 0.02 parts by mass, less than 0.01 parts by mass, and 0 parts by mass.

[0253] Examples of the mass % content (additive / electrical storage device binder aqueous solution) include less than 5 mass %, less than 4 mass %, less than 2 mass %, less than 1 mass %, less than 0.9 mass %, less than 0.5 mass %, less than 0.4 mass %, less than 0.2 mass %, less than 0.1 mass %, less than 0.09 mass %, less than 0.05 mass %, less than 0.04 mass %, less than 0.02 mass %, less than 0.01 mass %, and 0 mass %.

[0254] Examples of pH (electrical storage device binder aqueous solution) include 9, 8.5, 8, 7.5, 7, 6.5, and 6. In one embodiment, the pH is preferably 6 to 9.

[0255] The measurement conditions (pH) are as follows.

[0256] Measuring instrument: Product name: pH meter D-52, manufactured by Horiba, Ltd.

[0257] Measurement temperature: 25°C

[0258] By mixing the above agents, an aqueous solution of a power storage device binder can be produced.

[0259] Examples of the mixing means include a ball mill, a sand mill, a pigment disperser, a pestle, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.

[0260] Applications (electricity storage device binder aqueous solution) include, for example, an electrical storage device electrode binder aqueous solution, a battery electrode binder aqueous solution, a non-aqueous secondary battery electrode binder aqueous solution, a lithium ion battery electrode binder aqueous solution, a sodium ion battery electrode binder aqueous solution, an electrical storage device negative electrode binder aqueous solution, a battery negative electrode binder aqueous solution, a non-aqueous secondary battery negative electrode binder aqueous solution, a lithium ion battery negative electrode binder aqueous solution, a sodium ion battery negative electrode binder aqueous solution, an electrical storage device positive electrode binder aqueous solution, a battery positive electrode binder aqueous solution, a non-aqueous secondary battery positive electrode binder aqueous solution, a lithium ion battery positive electrode binder aqueous solution, a sodium ion battery positive electrode binder aqueous solution, an electrical storage device separator binder aqueous solution, a battery separator binder aqueous solution, a non-aqueous secondary battery separator binder aqueous solution, a lithium ion battery separator binder aqueous solution, a sodium ion battery separator binder aqueous solution, and the like.

[0261] [Electricity Storage Device Slurry: Slurry]

[0262] The present disclosure relates to a slurry for an electrical storage device.

[0263] The electrical storage device slurry comprises polyamic acid, water, and electrode active materials or non-conductive particles.

[0264] The polyamic acid comprises an aliphatic diamine unit,

[0265] The polyamic acid is an amine salt.

[0266] "Slurry" refers to a suspension of liquid and solid particles.

[0267] Examples of the polyamic acid, water, other binders, dispersion (emulsion), and thickener include those mentioned above.

[0268] Examples of the mass % content (polyamic acid / syrup) include 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.9 mass %, 0.7 mass %, 0.5 mass %, 0.3 mass %, and 0.1 mass %. In one embodiment, the content is preferably 0.1 to 10 mass %.

[0269] Examples of the mass % content (water / slurry) include 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, and 30 mass %. In one embodiment, the content is preferably 30 to 80 mass %.

[0270] Examples of the content (other binders), the content (dispersion (emulsion)), and the content (thickener) include the above-mentioned contents.

[0271] <Electrode active material>

[0272] In one embodiment, the electrical storage device slurry contains an electrode active material. Examples of the electrode active material include a negative electrode active material and a positive electrode active material. The electrode active material may be used alone or in combination of two or more.

[0273] (Negative electrode active material)

[0274] Examples of the negative electrode active material include carbon materials, materials alloyed with lithium, silicon materials, and oxides containing lithium atoms.

[0275] Examples of the carbon material include graphite, low-crystalline carbon, carbon black, fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon fibril, mesocarbon microbeads (MCMB), pitch-based carbon fiber, and activated carbon.

[0276] Examples of graphite include natural graphite and artificial graphite.

[0277] Examples of low-crystalline carbon include soft carbon and hard carbon.

[0278] Examples of carbon black include Ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black.

[0279] Examples of materials alloyed with lithium include lead compounds, tin compounds, arsenic compounds, antimony compounds, and aluminum compounds.

[0280] Examples of silicon materials include silicon, silicon oxide, silicon alloy, SiC, SiO x C y (0<x≦3, 0<y≦5), Si3N4, Si2N2O, SiO z (0<z≦2) etc.

[0281] Silicon oxide preferably includes combined SiO z Silicon oxide represented by (0<z≦2, preferably 0.1≦z≦1).

[0282] Examples of silicon alloys include silicon-titanium alloys, silicon-zirconium alloys, silicon-nickel alloys, silicon-copper alloys, silicon-iron alloys, and silicon-molybdenum alloys. In one embodiment, the silicon alloy is preferably a silicon-nickel alloy or a silicon-titanium alloy, more preferably a silicon-titanium alloy.

[0283] The mol% content (silicon atoms / total metal elements) is preferably 10 mol% or more, more preferably 20 mol% to 70 mol%.

[0284] Examples of the shape of the silicon material include single crystal, polycrystalline, and amorphous.

[0285] When a silicon material is used as the electrode active material, an electrode active material other than the silicon material may be used in combination.

[0286] Examples of electrode active materials other than silicon materials include carbon materials, conductive polymers, and composite metal oxides.

[0287] Examples of the conductive polymer include polyacene.

[0288] The composite metal oxide is represented by, for example, the following general formula.

[0289] A α B β O γ

[0290] (A represents an alkali metal or a transition metal. B represents at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese. O represents an oxygen atom. 0.05 < α < 1.10, 0.85 < β < 4.00, 1.5 < γ < 5.00)

[0291] Carbon materials undergo little volume change associated with the absorption and release of lithium. Therefore, when silicon materials are used as electrode active materials, they are preferably used in combination with carbon materials.

[0292] In one embodiment, preferred examples of the silicon material include carbon layer-coated silicon and carbon layer-coated silicon oxide.

[0293] Examples of the lithium atom-containing oxide include lithium-transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.

[0294] Examples of the lithium-transition metal composite oxide include lithium-manganese composite oxide, lithium-nickel composite oxide, lithium-cobalt composite oxide, lithium-iron composite oxide, lithium-titanium composite oxide, lithium-nickel-manganese composite oxide, and lithium-nickel-cobalt composite oxide.

[0295] In one embodiment, mass % content (carbon material and / or lithium alloyed material / negative electrode active material) is, for example, 100 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass % etc. In one embodiment, the content is preferably 50 mass % or more, more preferably 80 mass % or more, further preferably 90 mass % or more, and particularly preferably 100 mass %.

[0296] In one embodiment, the mass % content (carbon layer coated silicon and / or carbon layer coated silicon oxide / negative electrode active material) is, for example, 100 mass %, 90 mass % or more, 75 mass % or more, 50 mass % or more, 25 mass % or more, 10 mass % or more, 5 mass % or more, 2 mass % or more, 1 mass % or more, 0 mass %, etc.

[0297] In one embodiment, the mass % content (silicon material / negative electrode active material) is, for example, 100 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 0 mass %, etc.

[0298] (Positive electrode active material)

[0299] Examples of the positive electrode active material include positive electrode inorganic active materials and positive electrode organic active materials.

[0300] Examples of the positive electrode inorganic active material include transition metal oxides, lithium-transition metal composite oxides, transition metal sulfides, and activated carbon.

[0301] The inorganic active material may be partially substituted with an element. By allowing a carbon source to be present during reduction calcination, the inorganic active material can be used as a carbon material-coated electrode active material.

[0302] Examples of the positive electrode organic active material include conductive polymers.

[0303] Examples of the conductive polymer include polyacetylene and poly-p-phenylene.

[0304] (Physical properties, etc. (electrode active material))

[0305] Examples of the shape (electrode active material) include a microparticle shape and a thin film shape.

[0306] The average particle diameter (electrode active material) is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 45 μm, further preferably 1 μm to 10 μm, and particularly preferably 5 μm.

[0307] "Particle diameter" refers to the maximum distance between any two points on the particle's contour line. "Average particle diameter" refers to the value calculated as the average of the particle diameters of particles observed in several to dozens of fields of view using an observation method such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0308] The content (polyamic acid / electrode active material) in parts by mass is, for example, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1.5 parts by mass, 1 part by mass, 0.5 parts by mass, etc. In one embodiment, the content is preferably 0.5 to 15 parts by mass.

[0309] (Conductive additive)

[0310] In one embodiment, the slurry may optionally contain a conductive additive. The conductive additive may be used alone or in combination of two or more.

[0311] Examples of the conductive additive include fibrous carbon, carbon black, and metal fine powder.

[0312] Examples of fibrous carbon include vapor grown carbon fiber (VGCF), carbon nanotube (CNT), and carbon nanofiber (CNF).

[0313] Examples of carbon black include graphite particles, acetylene black, Ketjen black, and furnace black.

[0314] Examples of the metal fine powder include copper fine powder, nickel fine powder, aluminum fine powder, silicon fine powder, and alloy fine powder.

[0315] In one embodiment, the average particle size (metal fine powder) is preferably 10 μm.

[0316] The content (conductive aid / electrode active material) in parts by mass is preferably 0 to 10 parts by mass, more preferably 0 to 6 parts by mass.

[0317] <Non-conductive particles>

[0318] In one embodiment, the electrical storage device slurry includes non-conductive particles. The non-conductive particles may be used alone or in combination of two or more.

[0319] Examples of the non-conductive particles include oxide particles, nitride particles, covalent crystal particles, poorly soluble ion crystal particles, and clay fine particles.

[0320] Examples of oxide particles include aluminum oxide (alumina) particles, aluminum oxide hydrate (boehmite (AlOOH)) particles, gibbsite (Al(OH)3) particles, bakelite particles, iron oxide particles, silicon oxide particles, magnesium oxide (magnesia) particles, calcium oxide particles, titanium oxide (titania) particles, BaTiO3 particles, ZrO particles, aluminum oxide-silica composite oxide particles, etc.

[0321] Examples of the nitride particles include aluminum nitride particles, silicon nitride particles, and boron nitride particles.

[0322] Examples of covalent crystal particles include silicon particles and diamond particles.

[0323] Examples of the poorly soluble ion crystal particles include barium sulfate particles, calcium fluoride particles, and barium fluoride particles.

[0324] Examples of the clay fine particles include silica clay fine particles, talc clay fine particles, and montmorillonite clay fine particles.

[0325] In one embodiment, preferred examples of the non-conductive particles include boehmite particles, aluminum oxide particles, magnesium oxide particles, and barium sulfate particles.

[0326] Examples of the average particle diameter (non-conductive particles) include 30 μm, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm, and 0.01 μm. In one embodiment, the average particle diameter is preferably 0.01 μm to 30 μm.

[0327] Examples of the mass % content (non-conductive particles / paste) include 99.9 mass %, 95 mass %, 90 mass %, 80 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 1 mass %, 0.5 mass %, 0.2 mass %, and 0.1 mass %. In one embodiment, the content is preferably 0.1 mass % to 99.9 mass %.

[0328] Examples of the content (polyamic acid / non-conductive particles) in parts by mass include 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1.5 parts by mass, and 1 part by mass. In one embodiment, the content is preferably 1 to 15 parts by mass, more preferably 1.5 to 14 parts by mass, and even more preferably 2 to 12 parts by mass.

[0329] <Slurry viscosity adjustment solvent>

[0330] The slurry viscosity adjusting solvent may be used alone or in combination of two or more.

[0331] Examples of the slurry viscosity adjusting solvent include amide solvents, hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, amine solvents, lactone solvents, sulfoxide / sulfone solvents, and water.

[0332] Examples of the amide solvent include N-methylpyrrolidone, dimethylformamide, and N,N-dimethylacetamide.

[0333] Examples of the hydrocarbon solvent include toluene, xylene, n-dodecane, and tetralin.

[0334] Examples of the alcohol solvent include methanol, ethanol, 2-propanol, isopropanol, 2-ethyl-1-hexanol, 1-nonanol, and lauryl alcohol.

[0335] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, and isophorone.

[0336] Examples of the ether solvent include dioxane and tetrahydrofuran (THF).

[0337] Examples of the ester solvent include benzyl acetate, isoamyl butyrate, methyl lactate, ethyl lactate, and butyl lactate.

[0338] Examples of the amine solvent include o-toluidine, m-toluidine, and p-toluidine.

[0339] Examples of the lactone solvent include γ-butyrolactone and δ-butyrolactone.

[0340] Examples of the sulfoxide / sulfone solvent include dimethyl sulfoxide and sulfolane.

[0341] In one embodiment, the slurry viscosity adjusting solvent is preferably N-methylpyrrolidone.

[0342] Examples of the mass % content (slurry viscosity adjusting solvent / slurry) include 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 10 mass %.

[0343] <Slurry Additives>

[0344] The slurry may optionally contain any agent (slurry additive) not specified in any of the above. Examples of the slurry additive include the agents listed above.

[0345] Examples of the mass % content (slurry additive / slurry) include 0 mass % to 5 mass %, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, and 0 mass %.

[0346] The content in parts by mass (slurry additive / polyamic acid), the content in parts by mass (slurry additive / water), the content in parts by mass (slurry additive / other binders), the content in parts by mass (slurry additive / dispersion (emulsion)), the content in parts by mass (slurry additive / thickener), the content in parts by mass (slurry additive / electrode active material), the content in parts by mass (slurry additive / non-conductive particles), the content in parts by mass (slurry additive / slurry viscosity adjusting solvent) include, for example, 0 to 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc.

[0347] By mixing the agents, a slurry can be produced.

[0348] Examples of the mixing means include the aforementioned devices.

[0349] Examples of applications (electrical storage device slurry) include electrical storage device electrode slurry, battery electrode slurry, non-aqueous secondary battery electrode slurry, lithium ion battery electrode slurry, sodium ion battery electrode slurry, electrical storage device negative electrode slurry, battery negative electrode slurry, non-aqueous secondary battery negative electrode slurry, lithium ion battery negative electrode slurry, sodium ion battery negative electrode slurry, electrical storage device positive electrode slurry, battery positive electrode slurry, non-aqueous secondary battery positive electrode slurry, lithium ion battery positive electrode slurry, sodium ion battery positive electrode slurry, electrical storage device diaphragm slurry, battery diaphragm slurry, non-aqueous secondary battery diaphragm slurry, lithium ion battery diaphragm slurry, sodium ion battery diaphragm slurry, etc.

[0350] [Electrodes for electrical storage devices: Electrodes]

[0351] The present disclosure relates to an electric storage device electrode having a dried product of the electric storage device slurry on a current collector.

[0352] The electricity storage device electrode is obtained by applying the electricity storage device slurry on a current collector and drying the slurry.

[0353] Examples of the current collector include metal materials and carbon materials.

[0354] Examples of the metal material include copper, iron, aluminum, nickel, stainless steel, and nickel-plated steel.

[0355] Examples of the form of the metal material include metal foil, metal cylinder, metal coil, and metal plate.

[0356] Examples of the carbon material include carbon cloth and carbon paper.

[0357] Examples of the form (carbon material) include a carbon plate, a carbon thin film, and a carbon cylinder.

[0358] Examples of coating means include a knife coater, a gravure coater, a micro gravure coater, a die coater, and a bar coater.

[0359] The drying temperature is preferably 60°C to 200°C, more preferably 100°C to 195°C.

[0360] Examples of the dry atmosphere include dry air and an inert atmosphere.

[0361] The thickness (electrode (cured product)) is preferably 5 μm to 300 μm, more preferably 10 μm to 250 μm.

[0362] Examples of applications (electricity storage device electrodes) include electricity storage device positive electrodes, electricity storage device negative electrodes, battery electrodes, battery positive electrodes, battery negative electrodes, non-aqueous secondary battery electrodes, non-aqueous secondary battery positive electrodes, non-aqueous secondary battery negative electrodes, lithium ion battery electrodes, lithium ion battery positive electrodes, lithium ion battery negative electrodes, sodium ion battery electrodes, sodium ion battery positive electrodes, sodium ion battery negative electrodes, and the like.

[0363] [Electricity Storage Device Diaphragm: Diaphragm]

[0364] The present disclosure relates to an electric storage device separator comprising a dried product of the electric storage device slurry on a substrate.

[0365] The production (electricity storage device separator) can be performed by applying the electricity storage device separator slurry on one side or both sides of a substrate and drying the slurry.

[0366] Examples of the substrate include porous polyolefin resin substrates and plastic nonwoven fabrics.

[0367] (Porous polyolefin resin substrate)

[0368] The "porous polyolefin resin substrate" refers to a microporous membrane containing 30% by mass or more of a resin such as polyolefin, a mixture thereof, or a copolymer thereof.

[0369] The polyolefin resin may be used alone or in combination of two or more. Examples of the polyolefin resin include homopolymers and copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.

[0370] Examples of the stereostructure (polyolefin) include isotactic, syndiotactic, and atactic.

[0371] In one embodiment, the polyolefin resin is preferably high-density polyethylene, more preferably high-density polyethylene and polypropylene.

[0372] In one embodiment, the mass % content (polyolefin resin / substrate) is preferably 30% to 100% by mass, more preferably 40% to 100% by mass, and even more preferably 50% to 100% by mass.

[0373] The porous polyolefin resin substrate may optionally contain fillers or fiber compounds. The strength, hardness, and thermal shrinkage of the porous polyolefin resin substrate can be controlled by fillers or fiber compounds.

[0374] The porous polyolefin resin substrate may be surface-treated as needed.

[0375] Examples of the surface treatment include coating treatment, electromagnetic wire treatment, and plasma treatment.

[0376] In one embodiment, the surface treatment preferably includes coating with a polymer containing polar groups. The coating can improve the electrolyte impregnation and adhesion to the dried slurry. Examples of polar groups include carboxylic acid groups, hydroxyl groups, and sulfonic acid groups.

[0377] In one embodiment, the thickness (porous polyolefin resin substrate) is preferably 2 μm to 100 μm, more preferably 5 μm to 50 μm.

[0378] (Plastic non-woven fabric)

[0379] Examples of the plastic nonwoven fabric include nonwoven fabrics composed only of synthetic fibers.

[0380] Examples of synthetic fibers include polyolefin resins, polyester resins, acrylonitrile resins, polyamide resins, polyvinyl acetate resins, ethylene-vinyl acetate copolymer resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl ether resins, polyvinyl ketone resins, polyether resins, polyvinyl alcohol resins, diene resins, polyurethane resins, phenol resins, melamine resins, furan resins, urea resins, aniline resins, unsaturated polyester resins, alkyd resins, fluororesins, silicone resins, polyamide-imide resins, polyphenylene sulfide resins, polyimide resins, polycarbonate resins, polyazomethine resins, polyesteramide resins, polyetheretherketone resins, poly-p-phenylenebenzobisoxazole resins, polybenzimidazole resins, and ethylene-vinyl alcohol copolymer resins.

[0381] Examples of the polyolefin-based resin include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymer, and olefin-based copolymers.

[0382] Examples of polyester resins include polyethylene terephthalate (PET) resins, polybutylene terephthalate (PBT) resins, polytrimethylene terephthalate (PTT) resins, polyethylene naphthalate (PEN) resins, polybutylene naphthalate resins, polyethylene isophthalate resins, and wholly aromatic polyester resins.

[0383] Examples of the acrylonitrile-based resin include polyacrylonitrile and copolymers of acrylonitrile and a (meth)acrylic acid derivative, vinyl acetate, and the like.

[0384] Examples of the polyamide-based resin include aliphatic polyamide, wholly aromatic polyamide, and semi-aromatic polyamide.

[0385] Examples of aliphatic polyamides include nylon.

[0386] Examples of the wholly aromatic polyamide include poly-p-phenylene terephthalamide, poly-p-phenylene terephthalamide-3,4-diphenyl ether terephthalamide, and poly-m-phenylene isophthalamide.

[0387] The "semi-aromatic polyamide" refers to a polyimide in which a portion of the main chain of an aromatic polyamide is an aliphatic chain.

[0388] The plastic nonwoven fabric fibers may optionally contain fibers other than synthetic resin fibers.

[0389] Examples of fibers other than synthetic resin fibers include solvent-spun cellulose, fibrillated products of solvent-spun cellulose, regenerated cellulose, fibrillated products of regenerated cellulose, natural cellulose fibers, pulped products of natural cellulose fibers, fibrillated products of natural cellulose fibers, and inorganic fibers.

[0390] The mass % content (fibers other than synthetic fibers / nonwoven fabric) is preferably 50 mass % or less, more preferably 30 mass % or less, and even more preferably 10 mass % or less.

[0391] Examples of the form (morphology) include single fibers and composite fibers.

[0392] "Single fiber" refers to a fiber formed from a single resin. "Conjugate fiber" refers to a fiber formed from two or more resins.

[0393] Examples of the form (composite fiber) include a core-sheath type, an eccentric core type, a side-by-side type, an island-in-the-sea type, a segmented orange type, and a multi-bimetal type.

[0394] In one embodiment, the average fiber diameter (plastic nonwoven fabric) is preferably 1 μm to 15 μm, more preferably 1 μm to 10 μm.

[0395] The “average fiber diameter” refers to the average value of the fiber diameters of 20 fibers randomly selected from a scanning electron microscope photograph.

[0396] In one embodiment, the average pore diameter (plastic nonwoven fabric) is preferably 1 μm to 20 μm, more preferably 3 μm to 20 μm, and even more preferably 5 μm to 20 μm.

[0397] The "pore size" refers to the width of the gap between fibers. The "average pore size" refers to the average value of the pore sizes of 20 fibers randomly selected from a scanning electron microscope photograph.

[0398] In one embodiment, the thickness (plastic nonwoven fabric) is preferably 5 μm to 25 μm, more preferably 5 μm to 15 μm.

[0399] <Manufacturing method (electricity storage device diaphragm)>

[0400] Examples of the production method (electrical storage device separator) include a method including a coating step of coating the electrical storage device separator slurry on a substrate and a drying step of drying the coated electrical storage device separator slurry.

[0401] (Coating process)

[0402] Examples of the coating method include coating, printing, transfer, and dipping.

[0403] Examples of coating methods include doctor blades, rods, reverse rollers, lips, dies, curtains, and air knives.

[0404] Examples of printing methods include flexographic printing, screen printing, offset printing, gravure printing, and inkjet printing.

[0405] Examples of the transfer method include roller transfer and film transfer.

[0406] Examples of the impregnation method include dipping.

[0407] (Drying process)

[0408] Examples of the drying method include air drying, irradiation drying, and vacuum drying.

[0409] Examples of air drying include warm air drying, hot air drying, and low-humidity air drying.

[0410] Examples of irradiation drying include infrared ray irradiation drying, far infrared ray irradiation drying, and electron beam irradiation drying.

[0411] The drying temperature is preferably 40°C to 90°C, more preferably 50°C to 80°C.

[0412] The drying time is preferably 5 seconds to 3 minutes, more preferably 15 seconds to 2 minutes.

[0413] The production method (electricity storage device separator) may optionally include a pressurizing step.

[0414] Examples of the pressurizing means include a die press and a roller press.

[0415] Examples of applications (electricity storage device separators) include battery separators, non-aqueous secondary battery separators, lithium ion battery separators, and sodium ion battery separators.

[0416] [Electrode stack / separator]

[0417] The present disclosure relates to an electric storage device separator / electrode laminate having a dried product of the electric storage device slurry on the active material side of an electrode.

[0418] The electrical storage device separator / electrode laminate is obtained by applying the electrical storage device slurry to electrodes and drying the slurry.

[0419] Examples of the production method (electricity storage device separator / electrode stack) include a method including the following steps.

[0420] (1) Process of coating a slurry containing an electrode material on a current collector

[0421] (2) Step of drying the slurry containing the electrode material

[0422] (3) Step of Pressurizing the Dried Material of the Slurry Containing the Electrode Material

[0423] (4) Step of applying the storage device diaphragm slurry onto the dried product of the slurry containing the electrode material

[0424] (5) Drying process of storage device diaphragm slurry

[0425] Examples of the coating method, drying method, and pressurizing method include the methods described above.

[0426] Applications (electrical storage device separator / electrode stack) include, for example, battery separator / electrode stack, battery separator / negative electrode stack, battery separator / positive electrode stack, non-aqueous secondary battery separator / electrode stack, non-aqueous secondary battery separator / negative electrode stack, non-aqueous secondary battery separator / positive electrode stack, lithium-ion battery separator / electrode stack, lithium-ion battery separator / negative electrode stack, lithium-ion battery separator / positive electrode stack, sodium-ion battery separator / electrode stack, sodium-ion battery separator / negative electrode stack, sodium-ion battery separator / positive electrode stack, etc.

[0427] [Electricity Storage Equipment]

[0428] The present disclosure relates to an electric storage device.

[0429] In one embodiment, the electricity storage device includes the electricity storage device electrode.

[0430] In one embodiment, the electricity storage device includes the electricity storage device separator.

[0431] In one embodiment, the electrical storage device includes the electrical storage device separator / electrode stack.

[0432] (Electrolyte)

[0433] The electrical storage device may optionally contain an electrolyte solution. Examples of the electrolyte solution include a solution in which a supporting electrolyte is dissolved in a non-aqueous solvent.

[0434] The non-aqueous solvent may be used alone or in combination of two or more.

[0435] Examples of the non-aqueous solvent include chain carbonate solvents, cyclic carbonate solvents, chain ether solvents, cyclic ether solvents, chain ester solvents, cyclic ester solvents, and acetonitrile.

[0436] Examples of the chain carbonate solvent include diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.

[0437] Examples of the cyclic carbonate solvent include ethylene carbonate, propylene carbonate, and butylene carbonate.

[0438] Examples of the chain ether solvent include 1,2-dimethoxyethane.

[0439] Examples of the cyclic ether solvent include tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, and 1,3-dioxolane.

[0440] Examples of the chain ester solvent include methyl formate, methyl acetate, and methyl propionate.

[0441] Examples of the cyclic ester solvent include γ-butyrolactone and γ-valerolactone.

[0442] In one embodiment, the non-aqueous solvent preferably includes a combination of a cyclic carbonate and a chain carbonate.

[0443] The supporting electrolyte may be used alone or in combination of two or more.

[0444] Examples of supporting electrolytes include lithium salts. Examples of lithium salts include LiPF6, LiAsF6, LiBF4, LiSBF6, LiAlCl4, LiClO4, CF3SO3Li, C4F9SO3Li, CF3COOLi, (CF3CO)2NLi, (CF3SO2)2NLi, (C2F5SO2)NLi, etc. In one embodiment, the supporting electrolyte preferably includes LiPF6, LiClO4, and CF3SO3Li.

[0445] In one embodiment, the non-aqueous electrolyte solution may optionally contain a film-forming agent. The film-forming agent may be used alone or in combination of two or more.

[0446] Examples of the film-forming agent include carbonates, cyclosulfides, sultones, and acid anhydrides.

[0447] Examples of the carbonate ester include vinylene carbonate, vinylethylene carbonate, vinyl ethyl carbonate, methylphenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate.

[0448] Examples of alkyl sulfides include ethylene sulfide and propylene sulfide.

[0449] Examples of sultone include 1,3-propane sultone and 1,4-butane sultone.

[0450] Examples of the acid anhydride include maleic anhydride and succinic anhydride.

[0451] In one embodiment, the mass % content (film-forming agent / electrolyte) is preferably 10 mass % or less, more preferably 8 mass % or less, further preferably 5 mass % or less, and particularly preferably 2 mass % or less.

[0452] Examples of the form (electricity storage device) include a cylindrical type with spiral sheet electrodes and separators, a cylindrical type with an inside-out structure combining pellet electrodes and separators, and a coin type with laminated pellet electrodes and separators.

[0453] As a manufacturing method (electricity storage device), for example, there is a method described in Japanese Patent Application Laid-Open No. 2013-089437.

[0454] Examples of applications (electricity storage devices) include batteries, non-aqueous secondary batteries, lithium ion batteries, and sodium ion batteries.

[0455] Example

[0456] The present invention is described in detail below using examples and comparative examples. However, these descriptions and the following examples are not intended to limit the present invention. The present invention is limited only by the claims. Unless otherwise specified, all values ​​such as parts and percentages are by mass.

[0457] Example 1

[0458] To a glass reaction vessel (500 mL internal volume) equipped with a stirrer and nitrogen inlet and exhaust tubes, 153 g of water, 69.2 g of DMEA (equivalent to 1.25 times the equivalent of carboxyl groups), 35.32 g (0.248 mol) of 1,3-BAC, and 8.14 g (0.062 mol) of IBPA were added and stirred at 25°C for 5 minutes to dissolve them. To this solution, 100 g (0.31 mol) of BTDA was added, and the mixture was stirred at 70°C for 6 hours to obtain a polyamic acid aqueous solution (non-volatile content 34.9% by mass, solution viscosity 918 mPa·s).

[0459] Unless otherwise specified, other changes may be made as shown in the following table, and the same procedures as described above may be followed.

[0460] [Table 1]

[0461]

[0462] "Mol % (acid anhydride)" refers to a value based on 100 mol % of the acid anhydride.

[0463] "Mol % (diamine)" means a value based on 100 mol % of the diamine.

[0464] BTDA: 3,3',4,4'-Benzophenonetetracarboxylic dianhydride, product name "BTDA-PF," manufactured by Evonik Japan

[0465] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride, product name "BPDA," manufactured by Mitsubishi Chemical Co., Ltd.

[0466] 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, product name "6FDA," manufactured by Daikin Co., Ltd.

[0467] 1,3-BAC: 1,3-bisaminomethylcyclohexane, product name "1,3-BAC," manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0468] IBPA: 3,3'-diaminodipropylamine, manufactured by Guangrong Chemical Co., Ltd.

[0469] HMDA: Hexamethylenediamine, manufactured by INVISTA

[0470] MPDA: meta-phenylenediamine, manufactured by Sigma-Aldrich

[0471] 4,4-DPE: 4,4'-diaminodiphenyl ether, manufactured by Seika Co., Ltd.

[0472] DMEA: 2-(dimethylamino)ethanol, manufactured by Nippon Emulsifier Co., Ltd.

[0473] N100: N,N-dimethylcyclohexylamine, product name "Lupragen N100", manufactured by BASF

[0474] TMEDA: Tetramethylethylenediamine, manufactured by Guangrong Chemical Co., Ltd.

[0475] DMZ: 1,2-dimethylimidazole, manufactured by Shikoku Chemical Co., Ltd.

[0476] <Coating properties>

[0477] The electricity storage device binder aqueous solution was applied to the current collector copper foil using an applicator.

[0478] (Evaluation Criteria)

[0479] ○: No coating streaks or gaps were generated, and no aggregates were present.

[0480] ×: Coating streaks or gaps occurred, or aggregates were present.

[0481] <Adhesion>

[0482] An aqueous solution of a storage battery device binder was applied to a glass substrate using an applicator. The coated film was placed in a hot air dryer under normal pressure and heated at 80°C for 10 minutes, 120°C for 20 minutes, and 200°C for 30 minutes under reduced pressure to produce a 10 μm thick polyimide film (dried product). The polyimide film was then subjected to a crosshatch peel test.

[0483] Chessboard production method: cutting knife

[0484] Number of chessboard grids: 100

[0485] Checkerboard size: 1mm×1mm

[0486] Adhesive tape: Product name "Cellotape (registered trademark)", manufactured by Nichiban Co., Ltd.

[0487] Peeling direction: vertical direction (evaluation basis)

[0488] ○: The number of peeling is less than 9 mesh ×: The number of peeling is more than 10 mesh

Claims

1. An aqueous solution of an electrical storage device binder, The electrical storage device binder aqueous solution comprises polyamic acid and water, The polyamic acid comprises an aliphatic diamine unit, The polyamic acid is an amine salt.

2. The electrical storage device binder aqueous solution according to claim 1, wherein The polyamic acid includes polyamine units.

3. A slurry for an electrical storage device, The electrical storage device slurry comprises polyamic acid, water, and electrode active materials or non-conductive particles. The polyamic acid comprises an aliphatic diamine unit, The polyamic acid is an amine salt. 4 . An electrical storage device electrode comprising a dried product of the electrical storage device slurry according to claim 3 on a current collector. 5 . An electrical storage device separator comprising a dried product of the electrical storage device slurry according to claim 3 on a substrate. 6 . An electrical storage device separator / electrode laminate comprising the dried product of the electrical storage device slurry according to claim 3 on the active material side of an electrode. 7 . An electric storage device comprising one or more selected from the group consisting of the electric storage device electrode according to claim 4 , the electric storage device separator according to claim 5 , and the electric storage device separator / electrode laminate according to claim 6 .

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