Energy storage device aqueous solution, energy storage device slurry, energy storage device electrode, energy storage device separator, energy storage device separator / electrode laminate, energy storage device electrolyte and energy storage device

Abstract

To provide an aqueous solution for energy storage devices, a slurry for energy storage devices, electrodes for energy storage devices, separators for energy storage devices, separator / electrode stacks for energy storage devices, electrolytes for energy storage devices, and energy storage devices. [Solution] An aqueous solution for an energy storage device, wherein the aqueous solution for the energy storage device comprises a water-soluble polymer, and the water-soluble polymer comprises hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units.

Description

[Technical Field]

[0001] This disclosure relates to an aqueous solution for an energy storage device, a slurry for an energy storage device, an electrode for an energy storage device, a separator for an energy storage device, a separator / electrode laminate for an energy storage device, an electrolyte for an energy storage device, and an energy storage device. [Background technology]

[0002] The applicant is exploring a method of using water-soluble polymers as binders for energy storage devices. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2018-006333 [Overview of the project] [Problems that the invention aims to solve]

[0004] The problem that this invention aims to solve is to provide an aqueous solution for an energy storage device that can produce a slurry with good dispersibility and electrodes with good electrode flexibility and adhesion. [Means for solving the problem]

[0005] This disclosure provides the following items: (Item 1) Aqueous solution for an energy storage device, The aforementioned aqueous solution of the energy storage device contains a water-soluble polymer, The aforementioned water-soluble polymer is an aqueous solution for an energy storage device, comprising hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units. (Item 2) Energy storage device slurry, The energy storage device slurry comprises a water-soluble polymer and water. The above-mentioned water-soluble polymer is a power storage device slurry containing a hydroxyl group-containing (meth)acrylamide unit and an α,β-unsaturated nitrile unit. (Item 3) The power storage device slurry according to the above item, containing an electrode active material. (Item 4) The power storage device slurry according to the above item, containing non-conductive particles. (Item 5) A power storage device electrode having a dried product of the power storage device slurry according to any one of the above items on a current collector. (Item 6) A power storage device separator having a dried product of the power storage device slurry according to any one of the above items on a substrate. (Item 7) A power storage device separator / electrode laminate having a dried product of the power storage device slurry according to any one of the above items on the active material side of an electrode. (Item 8) A power storage device electrolyte which is a gelled product of the power storage device aqueous solution according to the above item. (Item 9) A power storage device including the power storage device electrode according to the above item. (Item 10) A power storage device including the power storage device separator according to the above item. (Item 11) A power storage device including the power storage device separator / electrode laminate according to the above item. (Item A power storage device including the power storage device electrolyte according to the above item.

[0006] In the present disclosure, the above-described one or more features may be provided in combination in addition to the explicitly stated combinations.

Advantages of the Invention

[0007] The slurry of the present invention exhibits good dispersibility. The electrode of the present invention exhibits good electrode flexibility and adhesion.

Modes for Carrying Out the Invention

[0008] Throughout this disclosure, the ranges of numerical values ​​such as physical properties and content may be set as appropriate (for example, by selecting from the values ​​listed in each of the items below). Specifically, if the numerical value α is such as A3, A2, A1 (A3 > A2 > A1), then the range of the numerical value α may be 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 A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less.

[0009] The components, conditions, numerical values, etc., are not particularly limited, as long as the problems that this invention aims to solve are resolved.

[0010] "αβ amount (A / B)" means the amount of β (α) of A relative to 100α of B. α can be expressed as mass%, mole%, or parts by mass, for example. β amount can be expressed as content, amount used, for example. "Mass% content (A / B)" means the content (mass%) of A relative to 100% mass of B.

[0011] "γ ratio (A / B)" refers to the γ ratio calculated using the formula "A ÷ B". Examples of γ ratios include mass ratios and molar ratios.

[0012] "Non-volatile content" refers to the total mass of components other than organic solvents and water. In one embodiment, "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C and a constant weight is reached.

[0013] "(meth)acrylic" means "acrylic and / or methacrylic". "(meth)acrylate" means "acrylate and / or methacrylate". "(meth)acryloyl" means "acryloyl and / or methacryloyl".

[0014] "(Meta)allyl" means "allyl and / or metallyl".

[0015] "C..." means "of the number of carbon atoms." For example, "C1-6 alkyl group" means an alkyl group with 1 to 6 carbon atoms. "C6 alkyl group" means an alkyl group with 6 carbon atoms.

[0016] Examples of alkyl groups include linear alkyl groups, branched alkyl groups, and cycloalkyl groups.

[0017] Examples of linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group.

[0018] Examples of branched alkyl groups include iso-propyl group, sec-butyl group, iso-butyl group, tert-butyl group, 2-ethylhexyl group, diethylpentyl group, trimethylbutyl group, trimethylpentyl group, and trimethylhexyl group.

[0019] Examples of cycloalkyl groups include monocyclic cycloalkyl groups, crosslinked ring cycloalkyl groups, and fused ring cycloalkyl groups. Furthermore, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also considered a cycloalkyl group.

[0020] A "monocyclic ring" refers to a cyclic structure formed by covalent bonds between carbon atoms that does not have an internal bridging structure. A "condensed ring" refers to a cyclic structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one edge with the others through condensation). A "bridging ring" refers to a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0021] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl groups.

[0022] Examples of crosslinked ring cycloalkyl groups include tricyclodecyl groups, adamantyl groups, norbornyl groups, and the like.

[0023] Alkyl groups also include combinations of linear alkyl groups, branched alkyl groups, and cycloalkyl groups. Examples of such combinations include cycloalkylalkyl groups.

[0024] Cycloalkylalkyl groups are represented by the following formula. R calkyl -R alkyl - (In the formula, R calkyl R represents a cycloalkyl group. alkyl (This represents an alkyl group.)

[0025] Examples of alkylene groups include linear alkylene groups, branched alkylene groups, and cycloalkylene groups.

[0026] Examples of linear alkylene groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decamethylene.

[0027] Examples of branched alkylene groups include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

[0028] Examples of cycloalkylene groups include monocyclic cycloalkylene groups, crosslinked ring cycloalkylene groups, and fused ring cycloalkylene groups. Furthermore, one or more hydrogen atoms in the cycloalkylene group may be substituted by a linear or branched alkyl group.

[0029] Examples of monocyclic cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0030] Examples of the bridged cycloalkylene group include a tricyclodecylene group, an adamantylene group, a norbornylene group, etc.

[0031] Examples of the fused cycloalkylene group include a bicyclodecylene group, etc.

[0032] The alkylene group includes a linear alkylene group, a branched alkylene group, and a group formed by combining a cycloalkylene group. Examples of the combined group include a cycloalkylenealkylene group, an alkylene cycloalkylene alkylene group, etc.

[0033] The cycloalkylenealkylene group is represented by the following formula. -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0034] The alkylene cycloalkylene alkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0035] The aromatic group (aryl group, arylene group) may or may not be substituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, a carbonylaryl group, etc.

[0036] Examples of the aryl group include a monocyclic aryl group, a fused-ring aryl group, etc.

[0037] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, a mesityl group, etc.

[0038] Examples of fused ring aryl groups include naphthyl groups.

[0039] Examples of arylene groups include monocyclic arylene groups and fused-ring arylene groups.

[0040] Examples of monocyclic arylene groups include phenylene groups and trilene groups.

[0041] Examples of fused ring arylene groups include naphthylene groups.

[0042] Examples of salts include inorganic salts and organic salts.

[0043] Examples of inorganic salts include sodium salts, lithium salts, calcium salts, and ammonium salts.

[0044] Examples of organic salts include amine salts.

[0045] [Energy storage device aqueous solution: aqueous solution] This disclosure relates to an aqueous solution for an energy storage device, The aforementioned aqueous solution of the energy storage device contains a water-soluble polymer, The water-soluble polymer in question is an aqueous solution for an energy storage device, comprising hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units.

[0046] <Water-soluble polymer: polymer> Water-soluble polymers can be used individually or in combination of two or more types.

[0047] "Water-soluble" means that when 0.5 g of the compound is dissolved in 100 g of water at 25°C, the water-insoluble portion is less than 0.5% by mass (less than 2.5 mg).

[0048] Examples of water-insoluble components include less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, less than 0.2% by mass, less than 0.1% by mass, and 0% by mass.

[0049] (Hydroxyl group-containing (meth)acrylamide) Hydroxyl group-containing (meth)acrylamides can be used alone or in combination of two or more types.

[0050] Examples of hydroxyl group-containing (meth)acrylamides include N-hydroxyalkyl (meth)acrylamide and N-hydroxyaryl (meth)acrylamide.

[0051] Examples of N-hydroxyalkyl(meth)acrylamides include N-hydroxyacyclicalkyl(meth)acrylamides and N-hydroxycycloalkyl(meth)acrylamides.

[0052] Examples of N-hydroxyacyclic alkyl(meth)acrylamides include N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(2-hydroxy-1,1-dimethylethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(1-ethyl-2-hydroxyethyl)(meth)acrylamide, N-(1-(hydroxymethyl)ethyl)(meth)acrylamide, N-(1-hydroxy-4-methylpentan-2-yl)(meth)acrylamide, N-(1-hydroxy-3-methylbutan-2-yl)(meth)acrylamide, and N-(2-(2-hydroxyethoxy)ethyl)(meth)acrylamide.

[0053] Examples of N-hydroxycycloalkyl(meth)acrylamides include No-hydroxycyclohexyl(meth)acrylamide, Nm-hydroxycyclohexyl(meth)acrylamide, Np-hydroxycyclohexyl(meth)acrylamide, N-(2,6-dimethyl-4-hydroxycyclohexyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxycyclohexyl)(meth)acrylamide, N-(2,4-dihydroxycyclohexyl)(meth)acrylamide, and N-(3,5-dihydroxycyclohexyl)(meth)acrylamide.

[0054] Examples of N-hydroxyaryl(meth)acrylamides include No-hydroxyphenyl(meth)acrylamide, Nm-hydroxyphenyl(meth)acrylamide, Np-hydroxyphenyl(meth)acrylamide, N-(2,6-dimethyl-4-hydroxyphenyl)(meth)acrylamide, N-(3,5-dimethyl-4-hydroxyphenyl)(meth)acrylamide, N-(2,4-dihydroxyphenyl)(meth)acrylamide, N-(3,5-dihydroxyphenyl)(meth)acrylamide, and N-(2-hydroxy-4-carboxyphenyl)(meth)acrylamide.

[0055] In one embodiment, the hydroxyl group-containing (meth)acrylamide is represented by the following formula. CH2=C(R ha1 )-NH-R ha2 -OH (R ha1 R represents a hydrogen atom or a methyl group. ha2 (The characters represent alkylene groups and arylene groups. Preferably, the alkylene group is a C2-C4 alkylene group.)

[0056] Examples of molar content (hydroxyl group-containing (meth)acrylamide units / water-soluble polymer) include 99 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, and 5 mol%. In one embodiment, the above content is preferably 5 mol% to 99 mol%, and more preferably 10 mol% to 95 mol%.

[0057] Examples of mass% content (hydroxyl group-containing (meth)acrylamide units / water-soluble polymer) include 99% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. In one embodiment, the above content is preferably 5% by mass to 99% by mass.

[0058] (α,β-unsaturated nitriles) α,β-unsaturated nitriles can be used alone or in combination of two or more types.

[0059] Examples of α,β-unsaturated nitriles include (meth)acrylonitrile, α-chlor(meth)acrylonitrile, α-ethyl(meth)acrylonitrile, and vinylidene cyanide.

[0060] Examples of mol% content (α,β-unsaturated nitrile units / water-soluble polymer) include 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2 mol%, and 1 mol%. In one embodiment, the above content is preferably 1 mol% to 60 mol%, and more preferably 5 mol% to 50 mol%.

[0061] Examples of mass% content (α,β-unsaturated nitrile units / water-soluble polymer) include 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 60% by mass.

[0062] ((meth)acrylamide unit) In one embodiment, the water-soluble polymer may optionally contain (meth)acrylamide units. (Meth)acrylamide may be used alone or in combination of two or more types.

[0063] Examples of mol% content ((meth)acrylamide units / water-soluble polymer) include 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 90 mol%, and more preferably 0 mol% to 40 mol%.

[0064] Examples of mass% content ((meth)acrylamide units / water-soluble polymer) include 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 90% by mass, more preferably 1% by mass to 85% by mass, even more preferably 2% by mass to 50% by mass, and particularly preferably 3% by mass to 40% by mass.

[0065] (Alkyl(meth)acrylamide unit) In one embodiment, the water-soluble polymer may optionally contain alkyl(meth)acrylamide units. Alkyl(meth)acrylamides may be used alone or in combination of two or more.

[0066] "Alkyl(meth)acrylamide" refers to a compound in which one or more hydrogen atoms directly bonded to the nitrogen atom of (meth)acrylamide are replaced by an unsubstituted alkyl group.

[0067] Examples of alkyl(meth)acrylamides include dialkyl(meth)acrylamides and monoalkyl(meth)acrylamides.

[0068] "Monoalkyl(meth)acrylamide" refers to a compound in which one hydrogen atom directly bonded to the nitrogen atom of (meth)acrylamide is replaced by an unsubstituted alkyl group.

[0069] Examples of monoalkyl(meth)acrylamides include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl(meth)acrylamide.

[0070] "Dialkyl(meth)acrylamide" refers to a compound in which two hydrogen atoms directly bonded to the nitrogen atom of (meth)acrylamide are replaced by an unsubstituted alkyl group.

[0071] Examples of dialkyl(meth)acrylamides include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dipropyl(meth)acrylamide.

[0072] Examples of mol% content (alkyl(meth)acrylamide units / water-soluble polymer) include 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably between 0 mol% and 95 mol%.

[0073] Examples of mass% content (alkyl(meth)acrylamide units / water-soluble polymer) include 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 95% by mass.

[0074] (Unsaturated carboxylic acid (salt)) In one embodiment, the water-soluble polymer may optionally contain unsaturated carboxylic acid (salt) units. The unsaturated carboxylic acid (salt) may be used alone or in combination of two or more.

[0075] Examples of unsaturated carboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

[0076] Examples of unsaturated carboxylate salts include inorganic salts of unsaturated carboxylates and organic salts of unsaturated carboxylates.

[0077] Examples of unsaturated carboxylic acid inorganic salts include alkali metal salts of unsaturated carboxylic acids, alkaline earth metal salts of unsaturated carboxylic acids, and ammonium salts of unsaturated carboxylic acids.

[0078] Examples of alkali metal salts of unsaturated carboxylates include sodium salts of unsaturated carboxylates and lithium salts of unsaturated carboxylates.

[0079] Examples of unsaturated sodium carboxylate salts include sodium (meth)acrylate, sodium crotonate, sodium maleate, sodium fumarate, and sodium itaconate.

[0080] Examples of lithium unsaturated carboxylate salts include lithium (meth)acrylate, lithium crotonic acid, lithium maleate, lithium fumarate, and lithium itaconate.

[0081] Examples of unsaturated carboxylate alkaline earth metal salts include unsaturated carboxylate calcium salts.

[0082] Examples of unsaturated calcium carboxylate salts include calcium (meth)acrylate, calcium crotonate, calcium maleate, calcium fumarate, and calcium itaconate.

[0083] Examples of unsaturated ammonium carboxylate salts include ammonium (meth)acrylate, ammonium crotonate, ammonium maleate, ammonium fumarate, and ammonium itaconate.

[0084] Examples of molar content (unsaturated carboxylic acid (salt) units / water-soluble polymer) include 79.9 mol%, 79 mol%, 75 mol%, 70 mol%, 67 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 17 mol%, 15 mol%, 14.5 mol%, 14 mol%, 12 mol%, 10 mol%, 5 mol%, 4.5 mol%, 4 mol%, 3 mol%, 2.5 mol%, 1 mol%, 0 mol%, etc. In one embodiment, the above content is preferably 0 mol% to 79 mol%, and more preferably 5 mol% to 40 mol%.

[0085] Examples of mass% content (unsaturated carboxylic acid (salt) units / water-soluble polymer) include 79.9% by mass, 79% by mass, 75% by mass, 70% by mass, 67% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 17% by mass, 15% by mass, 14.5% by mass, 14% by mass, 12% by mass, 10% by mass, 5% by mass, 4.5% by mass, 4% by mass, 3% by mass, 2.5% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 79% by mass.

[0086] The neutralization rate [amount of unsaturated carboxylate per unit / (amount of unsaturated carboxylate per unit + amount of unsaturated carboxylic acid per unit)] can be, for example, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, etc. In one embodiment, the neutralization rate is preferably between 10% and 100%.

[0087] (Hydroxyl group-containing monomers: Excluding hydroxyl group-containing (meth)acrylamide) In one embodiment, the water-soluble polymer may optionally contain hydroxyl group-containing monomer units. The hydroxyl group-containing monomers may be used alone or in combination of two or more.

[0088] Examples of hydroxyl group-containing monomers include hydroxyl group-containing (meth)acrylic acid esters and hydroxyl group-containing vinyl ethers.

[0089] Examples of hydroxyl group-containing (meth)acrylic acid esters include hydroxyl group-containing linear (meth)acrylic acid esters and hydroxyl group-containing branched (meth)acrylic acid esters.

[0090] Examples of hydroxyl group-containing linear (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0091] Examples of hydroxyl group-containing branched (meth)acrylic acid esters include 1-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 1-hydroxy-2-methylethyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxy-1-methylpropyl (meth)acrylate, 2-hydroxy-1-methylpropyl (meth)acrylate, 3-hydroxy-1-methylpropyl (meth)acrylate, 1-ethyl-2-hydroxyethyl (meth)acrylate, 1-hydroxy-2-methylpropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 3-hydroxy-2-methylpropyl (meth)acrylate, and 1,1-dimethyl-2-hydroxyethyl (meth)acrylate.

[0092] Examples of hydroxyl group-containing vinyl ethers include hydroxyalkyl vinyl ethers and polyalkylene glycol monovinyl ethers.

[0093] Examples of hydroxyalkyl vinyl ethers include hydroxylinear alkyl vinyl ethers, hydroxybranched alkyl vinyl ethers, and hydroxycycloalkyl vinyl ethers.

[0094] Examples of hydroxylinear alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 5-hydroxypentyl vinyl ether.

[0095] Examples of hydroxy-branched alkyl vinyl ethers include 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, and 4-hydroxy-2-methylbutyl vinyl ether.

[0096] Examples of hydroxycycloalkyl vinyl ethers include 4-hydroxycyclopentyl vinyl ether.

[0097] Examples of polyalkylene glycol monovinyl ethers include polymethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and polypropylene glycol monovinyl ether.

[0098] Examples of polymethylene glycol monovinyl ethers include dimethylene glycol monovinyl ether, trimethylene glycol monovinyl ether, tetramethylene glycol monovinyl ether, pentamethylene glycol monovinyl ether, hexamethylene glycol monovinyl ether, heptamethylene glycol monovinyl ether, octamethylene glycol monovinyl ether, nonamethylene glycol monovinyl ether, decamethylene glycol monovinyl ether, and the like.

[0099] Examples of polyethylene glycol monovinyl ethers include diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, hexaethylene glycol monovinyl ether, heptaethylene glycol monovinyl ether, octaethylene glycol monovinyl ether, nonaethylene glycol monovinyl ether, decaethylene glycol monovinyl ether, and the like.

[0100] Examples of polypropylene glycol monovinyl ethers include dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, hexapropylene glycol monovinyl ether, heptapropylene glycol monovinyl ether, octapropylene glycol monovinyl ether, nonapropylene glycol monovinyl ether, decapropylene glycol monovinyl ether, and the like.

[0101] Examples of molar content (hydroxyl group-containing monomer units / water-soluble polymer) include 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 80 mol%, more preferably 5 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%.

[0102] Examples of mass% content (hydroxyl group-containing monomer units / water-soluble polymer) include 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 85% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 25% by mass to 45% by mass.

[0103] (Unsaturated hydrocarbon sulfonic acid (salt)) In one embodiment, the water-soluble polymer may optionally contain unsaturated hydrocarbon sulfonic acid (salt) units. The unsaturated hydrocarbon sulfonic acid (salt) may be used alone or in combination of two or more.

[0104] "Unsaturated hydrocarbon sulfonic acid (salt)" refers to a sulfonic acid (salt) whose structure, aside from the sulfonic acid (salt) group, consists only of carbon and hydrogen atoms.

[0105] Examples of unsaturated hydrocarbon sulfonic acids (salts) include vinyl sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid, sodium vinyl sulfonate, sodium styrene sulfonate, and sodium (meth)allyl sulfonate.

[0106] Examples of mol% content (unsaturated hydrocarbon sulfonic acid (salt) units / water-soluble polymer) include 1.0 mol%, 0.95 mol%, 0.9 mol%, 0.85 mol%, 0.8 mol%, 0.75 mol%, 0.7 mol%, 0.65 mol%, 0.6 mol%, 0.55 mol%, 0.5 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, 0.3 mol%, 0.25 mol%, 0.20 mol%, 0.15 mol%, 0.10 mol%, 0.08 mol%, 0.06 mol%, 0.05 mol%, 0.03 mol%, 0.01 mol%, 0.009 mol%, 0.007 mol%, 0.005 mol%, 0.003 mol%, 0.001 mol%, 0 mol%, etc. In one embodiment, the above content is preferably 0 mol% to 1.0 mol%, more preferably less than 0.1 mol%, even more preferably less than 0.01 mol%, and particularly preferably 0 mol%.

[0107] The mass % content (unsaturated hydrocarbon sulfonic acid (salt) unit / water-soluble polymer) is, for example, 1.0 mass %, 0.95 mass %, 0.9 mass %, 0.85 mass %, 0.8 mass %, 0.75 mass %, 0.7 mass %, 0.65 mass %, 0.6 mass %, 0.55 mass %, 0.5 mass %, 0.45 mass %, 0.4 mass %, 0.35 mass % Mass%, 0.3 mass%, 0.25 mass%, 0.20 mass%, 0.15 mass%, 0.10 mass%, 0.08 mass%, 0.06 mass%, 0.05 mass%, 0.0 Examples include 3% by mass, 0.01% by mass, 0.009% by mass, 0.007% by mass, 0.005% by mass, 0.003% by mass, 0.001% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% to 1.0% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, and particularly preferably 0% by mass.

[0108] The neutralization rate [unit amount of unsaturated hydrocarbon sulfonate / (unit amount of unsaturated hydrocarbon sulfonate + unit amount of unsaturated hydrocarbon sulfonic acid)] can be, for example, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, etc. In one embodiment, the neutralization rate is preferably 10% to 100%.

[0109] (Alkoxyalkyl (meth)acrylate unit) In one embodiment, the water-soluble polymer may optionally contain alkoxyalkyl (meth)acrylate units. The alkoxyalkyl (meth)acrylates may be used alone or in combination of two or more types.

[0110] Examples of alkoxyalkyl (meth)acrylates include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 1-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 1-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 1-methoxybutyl ( Examples include meth)acrylate, ethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 1-ethoxypropyl (meth)acrylate, propoxymethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 1-propoxyethyl (meth)acrylate, butoxymethyl (meth)acrylate, etc.

[0111] Examples of molar content (alkoxyalkyl (meth)acrylate units / water-soluble polymer) include 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 40 mol%.

[0112] Examples of mass% content (alkoxyalkyl (meth)acrylate units / water-soluble polymer) include 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 60% by mass.

[0113] (Polyfunctional monomers) In one embodiment, the water-soluble polymer may optionally contain polyfunctional monomer units. The polyfunctional monomers may be used alone or in combination of two or more.

[0114] A "polyfunctional monomer" refers to a monomer that has two or more ethylenically unsaturated double bonds.

[0115] Examples of polyfunctional monomers include polyfunctional (meth)acrylamide compounds, tri(allyl group)-containing monomers, and tri((meth)acryloyl group)-containing triazines.

[0116] A "polyfunctional (meth)acrylamide compound" refers to a compound having two or more (meth)acrylamide groups. [ka] (In the formula, R 1 (This is either a hydrogen atom or a methyl group.)

[0117] Examples of polyfunctional (meth)acrylamide compounds include N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N-[tris(3-(meth)acrylamidepropoxymethyl)methyl](meth)acrylamide, N,N-bis(2-(meth)acrylamideethyl)(meth)acrylamide, N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bis(meth)acrylamide, and N,N-1,2-ethanediylbis{N-[2-((meth)acryloylamino)ethyl](meth)acrylamide}.

[0118] Examples of monomers containing a tri(allyl group) include triallyl isocyanurate, triallyl trimellitate, triallylamine, and triallyl(meth)acrylamide.

[0119] Examples of tri((meth)acryloyl group)-containing triazines include 1,3,5-tri((meth)acryloyl)-1,3,5-triazine and 1,3,5-tri((meth)acryloyl)hexahydro-1,3,5-triazine.

[0120] Examples of mol% content (polyfunctional monomer units / water-soluble polymer) include 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0.9 mol%, 0.7 mol%, 0.5 mol%, 0.3 mol%, 0.1 mol%, 0.05 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 10 mol%, and more preferably 0.05 mol% to 2 mol%.

[0121] Examples of mass% content (polyfunctional monomer units / water-soluble polymer) include 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.7% by mass, 0.5% by mass, 0.3% by mass, 0.1% by mass, 0.05% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 10% by mass, and more preferably 0.05% by mass to 2% by mass.

[0122] (Monomers other than those listed above: Other components) The above water-soluble polymer may optionally contain monomer units (other components) other than those described above. These other components may be used alone or in combination of two or more.

[0123] Other components include, for example, unsaturated phosphoric acid (salt), alkyl (meth)acrylic acid esters, conjugated dienes, aromatic vinyl compounds, and the like.

[0124] Examples of unsaturated phosphates (salts) include vinylphosphonic acid, vinyl phosphate, bis((meth)acryloyloxyethyl) phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, monomethyl-2-(meth)acryloyloxyethyl phosphate, and 3-(meth)acryloyloxy-2-hydroxypropane phosphate.

[0125] Examples of alkyl (meth)acrylic acid esters include linear alkyl (meth)acrylic acid esters, branched alkyl (meth)acrylic acid esters, and alicyclic alkyl (meth)acrylic acid esters.

[0126] Examples of linear alkyl (meth)acrylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.

[0127] Examples of branched alkyl (meth)acrylate esters include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0128] Examples of alicyclic alkyl (meth)acrylic acid esters include cyclohexyl (meth)acrylate.

[0129] Examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chlor-1,3-butadiene, substituted linear-conjugated pentadiene, and substituted and side-conjugated hexadiene.

[0130] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.

[0131] Examples of mass % content (other component units / water-soluble polymer) include less than 10% by mass, less than 9% by mass, less than 7% by mass, less than 5% by mass, less than 4% by mass, less than 2% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.7% by mass, less than 0.5% by mass, less than 0.4% by mass, less than 0.2% by mass, less than 0.1% by mass, and 0% by mass. In one embodiment, the above content is preferably less than 10% by mass, more preferably less than 5% by mass, even more preferably less than 1% by mass, and particularly preferably 0% by mass.

[0132] The mol% content (other component units / water-soluble polymer) can be, 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 above content is preferably less than 10 mol%, more preferably less than 5 mol%, even more preferably less than 1 mol%, and particularly preferably 0 mol%.

[0133] <Manufacturing method (water-soluble polymer)> Examples of manufacturing methods (water-soluble polymers) include radical polymerization. In one embodiment, the polymerization temperature is preferably 50°C to 100°C. In one embodiment, the polymerization time is preferably 1 hour to 10 hours.

[0134] Examples of radical polymerization initiators include azo initiators, persulfates, and redox polymerization initiators.

[0135] Examples of azo initiators include 2,2'-azobis-2-amidinopropane dihydrochloride.

[0136] Examples of persulfates include potassium persulfate and ammonium persulfate.

[0137] Examples of redox polymerization initiators include combination systems (persulfate and reducing agent).

[0138] Examples of reducing agents include sodium bisulfite.

[0139] The mass% amount used (radical polymerization initiator / monomer group) is preferably 0.05% to 5.0% by mass, and more preferably 0.1% to 3.0% by mass.

[0140] <Physical properties (water-soluble polymers), etc.> Examples of weight-average molecular weight (water-soluble polymer: Mw) include 6 million, 5.5 million, 5 million, 4.5 million, 4 million, 3.5 million, 3 million, 2.5 million, 2 million, 1.5 million, 1 million, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, and 100,000. In one embodiment, the above weight-average molecular weight (Mw) is preferably between 100,000 and 6 million, and more preferably between 350,000 and 6 million.

[0141] Examples of number-average molecular weights (water-soluble polymers: Mn) include 6 million, 5.5 million, 5 million, 4.5 million, 4 million, 3.5 million, 3 million, 2.5 million, 2 million, 1.5 million, 1 million, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 300,000, 200,000, 100,000, 50,000, and 10,000. In one embodiment, the above number-average molecular weight (Mn) is preferably 10,000 or more.

[0142] Examples of molecular weight distributions (water-soluble polymers: Mw / Mn) include 15, 14, 13, 11, 10, 9, 7.5, 5, 4, 3, 2.9, 2.5, 2, 1.5, 1.1, etc. In one embodiment, the above molecular weight distribution (Mw / Mn) is preferably 1.1 to 15.

[0143] The measurement conditions (weight-average molecular weight, number-average molecular weight) are as follows: • Measuring instrument: GPC (model number: HLC-8420) manufactured by Tosoh Corporation • Columns: TSKgel Guardcolum PWXL, TSK-GEL G4000, TSK-GEL α-M (all manufactured by Tosoh Corporation) • Eluent: 0.2M NaNO3 50mM phosphate buffer / acetonitrile = 90 / 10 (v / v) aqueous solution Column temperature: 40°C • Calibration curve: Standard polyethylene oxide - polyethylene glycol • Measured concentration: 0.10% by mass (concentration of water-soluble polymer) • Filter: Cellulose acetate cartridge filter (manufactured by Tosoh Corporation, MyShori Disc W-13-2, pore size 0.2 μm)

[0144] Type B viscosity (aqueous solution for energy storage devices, 25°C, 3% non-volatile content) is, for example, 10000 mPa·s, 9000 mPa·s, 8000 mPa·s, 7000 mPa·s, 6000 mPa·s, 5000 mPa·s, 4000 mPa·s, 3000 mPa·s, 2500 mPa·s, 2250 mPa·s, 2000 mPa·s, 1890 mPa·s. Examples include mPa·s, 1600mPa·s, 1200mPa·s, 1000mPa·s, 900mPa·s, 750mPa·s, 700mPa·s, 660mPa·s, 500mPa·s, 310mPa·s, 300mPa·s, 250mPa·s, 200mPa·s, 150mPa·s, 100mPa·s, 50mPa·s, etc. In one embodiment, the above-mentioned B-type viscosity is preferably 50mPa·s to 10000mPa·s, more preferably 300mPa·s to 2500mPa·s.

[0145] The measurement conditions (Type B viscosity) are as follows: Solid content concentration: 3% by mass Measurement temperature: 25℃ Type B Viscometer: Manufactured by Toki Sangyo Co., Ltd. Product name: "Type B Viscometer Model TVB-10" Viscosity less than 100 mPa·s: No. 1 rotor, rotation speed 60 rpm Viscosity 100 mPa·s to 1000 mPa·s: No. 2 rotor, rotation speed 30 rpm Viscosity over 1000 mPa·s to 2500 mPa·s: No. 2 rotor, rotation speed 12 rpm Viscosity over 2500 mPa·s to 10000 mPa·s: No. 3 rotor, rotation speed 12 rpm

[0146] Examples of glass transition temperatures (for water-soluble polymers) include 160°C, 155°C, 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 115°C, 110°C, 105°C, 100°C, 95°C, 90°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, 15°C, 10°C, 5°C, and 0°C. In one embodiment, the glass transition temperature is preferably 0°C or higher, and more preferably 30°C or higher.

[0147] Based on the glass transition temperature (homopolymer) and mass fraction (monomer), the glass transition temperature (water-soluble polymer) can be calculated using Fox's formula. 1 / Tg=(W1 / Tg1)+(W2 / Tg2)+(W3 / Tg3)+····+(W n / Tg n ) [In Fox's formula, Tg is the glass transition temperature (K) of the polymer being sought, W1~W n These are the mass fractions of each monomer, Tg1~Tg n This indicates the glass transition temperature (homopolymer) (K) of each monomer.

[0148] The glass transition temperature can be measured using methods such as DSC (Differential Scanning Calorimetry), DTA (Differential Thermal Analysis), and TMA (Thermomechanical Analysis). The following are possible measurement conditions (glass transition temperature). Temperature range: -100℃ to 300℃ Heating rate: 10℃ / min

[0149] The glass transition temperature (for homopolymers) may also be based on values ​​found in the literature. Examples of such literature include "Chemical Handbook, Basic Edition II, edited by the Chemical Society of Japan (5th revised edition)," p. 325. Examples of glass transition temperatures (for homopolymers) include the following temperatures. Acrylamide: 165℃ Acrylic acid: 106℃ Hydroxyethyl acrylate: -15℃ Acrylonitrile: 105℃

[0150] Examples of mass% content (water-soluble polymer / aqueous solution for energy storage devices) include 25% by mass, 20% by mass, 19% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 25% by mass.

[0151] <Water> Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.

[0152] Examples of mass percent content (water / aqueous solution of energy storage device) include 99.9% by mass, 99% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, and 75% by mass. In one embodiment, the above content is preferably 75% by mass to 99.9% by mass.

[0153] Examples of mass ratios (water-soluble polymer / 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, 0.05, etc. In one embodiment, the above mass ratio is preferably 0.05 to 0.33.

[0154] <Partial hydrolyzed condensates of polyalkoxysilanes: Partial hydrolyzed condensates> In one embodiment, the aqueous solution of the energy storage device may optionally contain a hydrolyzed partial condensate of a polyalkoxysilane. The hydrolyzed partial condensate may be used alone or in combination of two or more.

[0155] Examples of polyalkoxysilanes include trialkoxysilanes and tetraalkoxysilanes.

[0156] In one embodiment, the trialkoxysilane is represented by the following formula. [ka] (In the formula, R s1 R represents a substituted or unsubstituted alkyl group or alkenyl group. s2 ~R s4 Each of these independently represents an alkyl group.

[0157] A "substituted alkyl group" refers to an alkyl group in which the hydrogen atoms constituting the alkyl group are replaced by groups other than hydrogen atoms or alkyl groups.

[0158] Examples of substituents include amino groups, mercapto groups, isocyanate groups, and (meth)acryloyloxy groups.

[0159] An amino group (an amino group-containing group) is represented by the following formula. -NR am1 R am2 (R am1 ~R am2 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group.

[0160] Examples of amino group-containing trialkoxysilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

[0161] Examples of mercapto group-containing trialkoxysilanes include 3-mercaptopropyltrimethoxysilane.

[0162] Examples of isocyanate group-containing trialkoxysilanes include 3-isocyanatetopropyltriethoxysilane.

[0163] Examples of trialksoxysilanes containing a (meth)acryloyloxy group include 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane.

[0164] Examples of alkenyl groups include vinyl groups and allyl groups.

[0165] Examples of alkenyl group-containing trialkoxysilanes include vinyltrimethoxysilane and vinyltriethoxysilane.

[0166] Examples of tetraalkoxysilanes include tetramethoxysilane, tetramethoxysilane oligomer, tetraethoxysilane, and tetraethoxysilane oligomer.

[0167] "Partial hydrolyzed condensate of polyalkoxysilane" refers to a hydrolyzed condensate that contains an alkoxy group. From the perspective of not gelling, the term "partial hydrolyzed condensate of polyalkoxysilane" is used instead of "complete hydrolyzed condensate of polyalkoxysilane."

[0168] Examples of condensation degrees (hydrolyzed partial condensates) include 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 19, 17, 15, 14, 13, 12, 11, 10, 9, 5, 3, 2, 1.7, 1.5, 1.4, 1.2, 1.1, and 1.01. In one embodiment, the above condensation degrees are preferably 1.01 to 1000, and more preferably 1.01 to 100.

[0169] Examples of weight-average molecular weights (hydrolyzed partial condensates) include 190,000, 170,000, 150,000, 130,000, 100,000, 90,000, 70,000, 50,000, 30,000, 20,000, 10,000, 9,000, 7,500, 5,000, 2,500, 1,000, 900, 750, 500, 250, 200, 175, 160, 150, 125, 110, and 100. In one embodiment, the above weight-average molecular weight is preferably between 100 and 190,000.

[0170] A partially condensed hydrolyzed polyalkoxysilane can be produced by hydrolyzing 100 parts by mass of polyalkoxysilane in the presence of 0 to 5 parts by mass of an acid catalyst or a base catalyst (preferably an acid catalyst) at a reaction temperature of 30°C to 60°C for 0.5 to 5.0 hours, thereby partially condensing it.

[0171] Examples of acid catalysts include nitric acid, hydrochloric acid, sulfurous acid, phosphoric acid, formic acid, and acetic acid.

[0172] Examples of base catalysts include sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, and amine compounds.

[0173] Examples of mass% content (hydrolyzed partial condensate / aqueous solution of energy storage device) include 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4.5% by mass, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.1% by mass, 0.09% by mass, 0.05% by mass, 0.03% by mass, 0.01% by mass, 0% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 10% by mass.

[0174] <Other Binders> In one embodiment, the aqueous solution of the energy storage device may optionally contain a binder other than a water-soluble polymer (other binder). The other binder may be used alone or in combination of two or more.

[0175] Other binders include, for example, diene copolymers, fluorine copolymers, amide-imide copolymers, and copolymers other than those mentioned above.

[0176] Examples of diene copolymers include styrene-butadiene copolymers, polybutadiene polymers, acrylonitrile-butadiene copolymers, methyl methacrylate-butadiene copolymers, and carboxy-modified styrene-butadiene copolymers.

[0177] Examples of fluorine-based copolymers include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE).

[0178] Examples of amide-imide copolymers include polyamides (PA), polyimides (PI), polyamide-imides (PAI), and aromatic polyamides.

[0179] Other copolymers include, for example, polyurethane polymers, poly(meth)acrylate polymers, vinyl chloride polymers, vinyl acetate polymers, vinyl acetate-ethylene copolymers, polyethylene, polypropylene, polyethylene terephthalate, polystyrene polymers, alginic acid (salt), and the like.

[0180] Examples of parts by mass content (other binders / water-soluble polymers) include 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 above content is preferably 0 to 100 parts by mass.

[0181] <Dispersion (Emulsion)> In one embodiment, the aqueous solution of the energy storage device may optionally contain a dispersion (emulsion). The dispersion (emulsion) may be used alone or in combination of two or more types.

[0182] Dispersions (emulsions) include, for example, 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 emulsion, vinyl acetate-ethylene copolymer emulsion, polyethylene emulsion, carboxy-modified styrene Examples include ombutadiene copolymer resin emulsion, acrylic resin emulsion, polyethylene, polypropylene, polyethylene terephthalate, polyamide (PA), polyimide (PI), polyamideimide (PAI), aromatic polyamide, alginic acid (salt), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), and the like.

[0183] Examples of the parts by mass content (dispersion (emulsion) / water-soluble polymer) include 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 above content is preferably 0 to 100 parts by mass.

[0184] <Thickening agent> In one embodiment, the aqueous solution of the energy storage device may optionally contain a thickening agent. The thickening agent may be used alone or in combination of two or more.

[0185] Examples of thickeners include cellulose polymers (salts), polyvinyl alcohols, (modified) poly(meth)acrylic acid (salts), polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, starch oxide, starch phosphate, casein, modified starch, and acrylonitrile-butadiene copolymer hydrogenates.

[0186] Examples of cellulose-based polymers (salts) include carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose.

[0187] Examples of polyvinyl alcohols include copolymers of (anhydrous) maleic acid and / or fumaric acid with vinyl alcohol.

[0188] Examples of the parts by mass content (thickener / water-soluble polymer) include 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 above content is preferably 0 to 100 parts by mass.

[0189] <Additives> The energy storage device aqueous solution may optionally contain agents (additives) that do not fall under any of the above categories. Additives may be used alone or in combination of two or more types.

[0190] Examples of additives include dispersants, leveling agents, and antioxidants.

[0191] Examples of dispersants include anionic dispersants, cationic dispersants, nonionic dispersants, and polymeric dispersants.

[0192] Examples of leveling agents include surfactants.

[0193] Examples of surfactants include alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.

[0194] Antioxidants include, for example, phenol compounds, hydroquinone compounds, organophosphorus compounds, sulfur compounds, phenylenediamine compounds, and polymer-type phenol compounds.

[0195] "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, and more preferably 600 to 700.

[0196] Examples of the parts by mass content (additive / water-soluble polymer) 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, 0 parts by mass, etc.

[0197] Examples of mass percent content (additive / aqueous solution of energy storage device) include less than 5 mass percent, less than 4 mass percent, less than 2 mass percent, less than 1 mass percent, less than 0.9 mass percent, less than 0.5 mass percent, less than 0.4 mass percent, less than 0.2 mass percent, less than 0.1 mass percent, less than 0.09 mass percent, less than 0.05 mass percent, less than 0.04 mass percent, less than 0.02 mass percent, less than 0.01 mass percent, 0 mass percent, etc.

[0198] Examples of pH values ​​for the aqueous solution of the energy storage device include 9, 8.9, 8.5, 8, 7.9, 7.5, 7, 6.9, 6.5, 6, 5.9, 5.6, 5.5, 5.4, 5.2, 5.1, and 5. In one embodiment, the above pH values ​​are preferably 5 to 9, and more preferably 5 to 7.

[0199] The following conditions can be used for measurement (pH). Measuring instrument: Manufactured by Horiba, Ltd. Product name: "pH meter D-52" Measurement temperature: 25℃

[0200] Applications (aqueous solutions for energy storage devices) include, for example, aqueous solutions for energy storage device electrode binders, battery electrode binders, non-aqueous secondary battery electrode binders, lithium-ion battery electrode binders, sodium-ion battery electrode binders, aqueous solution for energy storage device negative electrode binders, battery negative electrode binders, non-aqueous secondary battery negative electrode binders, lithium-ion battery negative electrode binders, sodium-ion battery negative electrode binders, aqueous solution for energy storage device positive electrode binders, battery positive electrode binders, non-aqueous secondary battery positive electrode binders, lithium-ion battery positive electrode binders, sodium-ion battery positive electrode binders, aqueous solution for energy storage device separator binders, battery separator binders, non-aqueous secondary battery separator binders, lithium-ion battery separator binders, sodium-ion battery separator binders, electrolyte solutions for energy storage devices, battery electrolyte solutions, non-aqueous secondary battery electrolyte solutions, lithium-ion battery electrolyte solutions, sodium-ion battery electrolyte solutions, etc.

[0201] [Energy storage device slurry: Slurry] This disclosure relates to an energy storage device slurry, The energy storage device slurry comprises a water-soluble polymer and water. The water-soluble polymer relates to an energy storage device slurry containing hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units.

[0202] "Slurry" refers to a suspension of liquid and solid particles.

[0203] Examples of water-soluble polymers, water, hydrolyzed partial condensates of polyalkoxysilanes, other binders, dispersions (emulsions), and thickeners include the substances mentioned above.

[0204] Examples of mass% content (water-soluble polymer / slurry) include 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.7% by mass, 0.5% by mass, 0.3% by mass, 0.1% by mass, etc. In one embodiment, the above content is preferably 0.1% by mass to 10% by mass.

[0205] Examples of mass% content (water / slurry) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, and 30% by mass. In one embodiment, the above content is preferably 30% by mass to 80% by mass.

[0206] Examples of mass% content (hydrolyzed partial condensate / slurry) include 5% by mass, 4.5% by mass, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.1% by mass, 0.09% by mass, 0.05% by mass, 0.03% by mass, 0.01% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass.

[0207] Examples of the amounts of other binders, dispersions (emulsions), and thickeners mentioned above include the amounts of the above-mentioned components.

[0208] <Electrode active material> In one embodiment, the energy storage device slurry may optionally include an electrode active material. Examples of electrode active materials include a negative electrode active material, a positive electrode active material, and so on. The electrode active materials may be used alone or in combination of two or more types.

[0209] (Negative electrode active material) Examples of negative electrode active materials include carbon materials, materials that alloy with lithium, silicon materials, and lithium atom-containing oxides.

[0210] Carbon materials include, for example, graphite, low-crystalline carbon, carbon black, fullerene, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon fibril, mesocarbon microbeads (MCMB), pitch-based carbon fiber, activated carbon, etc.

[0211] Graphite includes, for example, natural graphite, artificial graphite, etc.

[0212] Low-crystalline carbon includes, for example, soft carbon, hard carbon, etc.

[0213] Carbon black includes, for example, ketjen black, acetylene black, channel black, lamp black, oil furnace black, thermal black, etc.

[0214] Materials alloyed with lithium include, for example, lead compounds, tin compounds, arsenic compounds, antimony compounds, aluminum compounds, etc.

[0215] Silicon materials include, for example, silicon, silicon oxide, silicon alloy, SiC, SiO x C y (0 < x ≤ 3, 0 < y ≤ 5), Si3N4, Si2N2O, SiO z (0 < z ≤ 2), etc.

[0216] Silicon oxide preferably includes silicon oxide represented by the composition formula SiO z (0 < z ≤ 2, preferably 0.1 ≤ z ≤ 1).

[0217] Silicon alloys include, for example, silicon-titanium alloy, silicon-zirconium alloy, silicon-nickel alloy, silicon-copper alloy, silicon-iron alloy, silicon-molybdenum alloy, etc. In one embodiment, the silicon alloy preferably includes silicon-nickel alloy, silicon-titanium alloy, and more preferably silicon-titanium alloy.

[0218] The molar content (silicon atoms / total metal elements) is preferably 10 mol% or more, and more preferably 20 mol% to 70 mol%.

[0219] Examples of silicon material shapes include single crystal, polycrystalline, and amorphous materials.

[0220] When silicon material is used as the electrode active material, other electrode active materials may be used in combination.

[0221] Examples of electrode active materials other than silicon include carbon materials, conductive polymers, and composite metal oxides.

[0222] Carbon materials exhibit small volume changes associated with the intercalation and deintercalation of lithium. Therefore, when using silicon materials as electrode active materials, it is preferable to use them in combination with carbon materials.

[0223] Examples of conductive polymers include polyacene.

[0224] A composite metal oxide can be represented, for example, by the following general formula. A α B β O γ (A represents an alkali metal or transition metal. B represents at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese. O represents an oxygen atom. α, β, and γ are independently 0.05 < α < 1.10, 0.85 < β < 4.00, and 1.5 < γ < 5.00, respectively.)

[0225] In one embodiment, the silicon material preferably includes silicon covered with a carbon layer and silicon oxide covered with a carbon layer.

[0226] Examples of lithium atom-containing oxides include lithium-transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.

[0227] Examples of lithium-transition metal composite oxides 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.

[0228] In one embodiment, the mass% content (carbon material and / or material alloyed with lithium / negative electrode active material) can be, for example, 100% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 0% by mass, etc. In one embodiment, the above content can be preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0229] In one embodiment, the mass% content (carbon-coated silicon and / or carbon-coated silicon oxide / negative electrode active material) can be, for example, 100% by mass, 90% or more by mass, 75% or more by mass, 50% or more by mass, 25% or more by mass, 10% or more by mass, 5% or more by mass, 2% or more by mass, 1% or more by mass, 0% by mass, etc.

[0230] In one embodiment, the mass% content (silicon material / anode active material) can be, for example, 100% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 0% by mass, etc.

[0231] (Cathode active material) Examples of positive electrode active materials include positive electrode inorganic active materials and positive electrode organic active materials.

[0232] Examples of the cathode inorganic active material include transition metal oxides, lithium-transition metal composite oxides, transition metal sulfides, and activated carbon.

[0233] Inorganic active materials can be partially elementally substituted. By including a carbon source material during reduction firing, inorganic active materials can be used as electrode active materials covered with carbon materials.

[0234] Examples of positive electrode organic active materials include conductive polymers.

[0235] Examples of conductive polymers include polyacetylene and poly-p-phenylene.

[0236] (Physical properties, etc. (electrode active material)) Examples of the shape (electrode active material) include particulate matter and thin film.

[0237] The average particle size (electrode active material) is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 45 μm, even more preferably 1 μm to 10 μm, and particularly preferably 5 μm.

[0238] "Particle diameter" refers to the maximum distance between any two points on the contour line of a particle. "Average particle diameter" refers to the value calculated as the average particle diameter of particles observed within several to tens of fields of view using observation methods such as scanning electron microscopes (SEM) or transmission electron microscopes (TEM).

[0239] The amounts of parts by mass of the water-soluble polymer / electrode active material 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, 1 part by mass, 0.5 parts by mass, and the like. In one embodiment, the above amounts are preferably 0.5 to 15 parts by mass.

[0240] (Conductive additive) In one embodiment, the slurry may optionally contain a conductive aid. The conductive aid may be used alone or in combination of two or more kinds.

[0241] Examples of the conductive aid include fibrous carbon, carbon black, fine metal powder, etc.

[0242] Examples of the fibrous carbon include vapor grown carbon fiber (VGCF), carbon nanotube (CNT), carbon nanofiber (CNF), etc.

[0243] Examples of the carbon black include graphite particles, acetylene black, ketjen black, furnace black, etc.

[0244] Examples of the fine metal powder include fine copper powder, fine nickel powder, fine aluminum powder, fine silicon powder, fine alloy powder, etc.

[0245] In one embodiment, the average particle diameter (fine metal powder) is preferably 10 μm.

[0246] The content by mass part (conductive aid / electrode active material) is preferably 0 to 10 parts by mass, more preferably 0 to 6 parts by mass.

[0247] <Non-conductive particles> In one embodiment, the power storage device slurry may optionally contain non-conductive particles. The non-conductive particles may be used alone or in combination of two or more kinds.

[0248] Examples of the non-conductive particles include oxide particles, hydroxide particles, nitride particles, covalent crystal particles, hardly soluble ionic crystal particles, clay fine particles, aluminum particles, barium particles, calcium particles, etc.

[0249] Examples of oxide particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al(OH)3), bakelite, iron oxide, silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania), BaTiO3, ZrO, and alumina-silica composite oxides.

[0250] Examples of hydroxide particles include calcium hydroxide and magnesium hydroxide.

[0251] Examples of nitride particles include aluminum nitride, silicon nitride, and boron nitride.

[0252] Examples of covalent crystalline particles include silicon and diamond.

[0253] Examples of sparingly soluble ionic crystal particles include barium sulfate, calcium fluoride, and barium fluoride.

[0254] Examples of clay microparticles include silica, talc, montmorillonite, and other clay microparticles.

[0255] Examples of aluminum particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al(OH)3), aluminum nitride, etc.).

[0256] Examples of barium particles include barium sulfate and barium fluoride.

[0257] Examples of calcium particles include calcium hydroxide, magnesium hydroxide, and calcium fluoride.

[0258] In one embodiment, the non-conductive particles are preferably boehmite, alumina, magnesium oxide, and barium sulfate.

[0259] Examples of average particle diameters (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, 0.01 μm, etc. In one embodiment, the above average particle diameter is preferably 0.01 μm to 30 μm.

[0260] Examples of mass% content (non-conductive particles / slurry) include 99.9% by mass, 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, and 0% by mass. In one embodiment, the above content is preferably between 0% by mass and 99.9% by mass.

[0261] Examples of the parts by mass content (water-soluble polymer / non-conductive particles) 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, 1 part by mass, and so on. In one embodiment, the above 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.

[0262] <Slurry viscosity adjusting solvent> In one embodiment, the energy storage device slurry may optionally contain a slurry viscosity adjusting solvent. The slurry viscosity adjusting solvent may be used alone or in combination of two or more.

[0263] Examples of slurry viscosity adjusting solvents include amide solvents, hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, amine solvents, lactone solvents, sulfoxide / sulfone solvents, and water.

[0264] Examples of amide solvents include N-methylpyrrolidone, dimethylformamide, and N,N-dimethylacetamide.

[0265] Hydrocarbon solvents include, for example, toluene, xylene, n-dodecane, tetralin, etc.

[0266] Alcohol solvents include, for example, methanol, ethanol, 2-propanol, isopropyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol, etc.

[0267] Ketone solvents include, for example, acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, isophorone, etc.

[0268] Ether solvents include, for example, dioxane, tetrahydrofuran (THF), etc.

[0269] Ester solvents include, for example, benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, butyl lactate, etc.

[0270] Amine solvents include, for example, o-toluidine, m-toluidine, p-toluidine, etc.

[0271] Lactone solvents include, for example, γ-butyrolactone, δ-butyrolactone, etc.

[0272] Sulfoxide·sulfone solvents include, for example, dimethyl sulfoxide, sulfolane, etc.

[0273] In one embodiment, the slurry viscosity adjusting solvent is preferably N-methylpyrrolidone.

[0274] The mass% content (slurry viscosity adjusting solvent / slurry) includes, for example, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the above content is preferably 0 mass% to 10 mass%.

[0275] <Additive> The slurry described above may optionally contain agents (additives) that do not fall under any of the above categories. Examples of additives include the agents mentioned above.

[0276] Examples of mass percentage content (additive / slurry) include 0% to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0% by mass.

[0277] Examples of mass percentage content (additive / water-soluble polymer) include 0% to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc.

[0278] Examples of mass percentage content (additive / water) include 0% to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc.

[0279] Examples of mass percentage content (additive / electrode active material) include 0% to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0% by mass.

[0280] Examples of mass percentage content (additives / non-conductive particles) include 0% to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, and 0% by mass.

[0281] A slurry can be produced by dispersing and mixing the above agents.

[0282] Mixing means (slurry) include, for example, ball mills, sand mills, pigment dispersers, grinders, ultrasonic dispersers, homogenizers, planetary mixers, Hobart mixers, and the like.

[0283] Applications (energy storage device slurry) include, for example, energy storage device electrode slurry, battery electrode slurry, non-aqueous secondary battery electrode slurry, lithium-ion battery electrode slurry, sodium-ion battery electrode slurry, energy 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, energy 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, energy storage device separator slurry, battery separator slurry, non-aqueous secondary battery separator slurry, lithium-ion battery separator slurry, sodium-ion battery separator slurry, etc.

[0284] [Energy storage device electrodes: electrodes] This disclosure relates to an electrode for an energy storage device having a dried material of the above-mentioned energy storage device slurry on a current collector.

[0285] The energy storage device electrode is obtained by applying the above-mentioned energy storage device slurry to a current collector and drying it.

[0286] Examples of current collectors include metal materials and carbon materials.

[0287] Examples of metallic materials include copper, iron, aluminum, nickel, stainless steel, and nickel-plated steel.

[0288] Examples of forms (metallic materials) include metal foil, metal cylinders, metal coils, and metal plates.

[0289] Examples of carbon materials include carbon cloth and carbon paper.

[0290] Examples of forms (carbon materials) include carbon plates, carbon thin films, and carbon cylinders.

[0291] Coating methods include, for example, comma coaters, gravure coaters, microgravure coaters, die coaters, bar coaters, and the like.

[0292] The drying temperature is preferably 60°C to 200°C, and more preferably 70°C to 195°C.

[0293] Examples of a dry atmosphere include dry air and an inert atmosphere.

[0294] The thickness (electrode (cured material)) is preferably 5 μm to 300 μm, and more preferably 10 μm to 250 μm.

[0295] Applications (electrodes for energy storage devices) include, for example, positive electrodes for energy storage devices, negative electrodes for energy storage devices, battery electrodes, positive electrodes for batteries, negative electrodes for batteries, electrodes for non-aqueous secondary batteries, positive electrodes for non-aqueous secondary batteries, negative electrodes for non-aqueous secondary batteries, electrodes for lithium-ion batteries, positive electrodes for lithium-ion batteries, negative electrodes for lithium-ion batteries, electrodes for sodium-ion batteries, positive electrodes for sodium-ion batteries, negative electrodes for sodium-ion batteries, etc.

[0296] [Energy Storage Device Separator: Separator] This disclosure relates to an energy storage device separator having a dried material of the above-mentioned energy storage device slurry on a substrate.

[0297] The above-mentioned energy storage device separator can be manufactured by applying the energy storage device separator slurry to one or both sides of a substrate and drying it.

[0298] Examples of substrates include porous polyolefin resin substrates and plastic nonwoven fabrics.

[0299] (Porous polyolefin resin substrate) "Porous polyolefin resin substrate" means a microporous membrane containing 30% by mass or more of a resin such as polyolefins and mixtures or copolymers thereof.

[0300] Polyolefin resins can be used alone or in combination of two or more types. Examples of polyolefin resins include homopolymers and copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.

[0301] Examples of three-dimensional structures (polyolefins) include isotactic, syndiotactic, and atactic structures.

[0302] In one embodiment, the polyolefin resin is preferably high-density polyethylene, and more preferably high-density polyethylene and polypropylene.

[0303] 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.

[0304] Porous polyolefin resin substrates may optionally contain fillers and fibrous compounds. The strength, hardness, and thermal shrinkage of porous polyolefin resin substrates can be controlled by the fillers and fibrous compounds.

[0305] Porous polyolefin resin substrates may be surface-treated as needed.

[0306] Examples of surface treatments include coating, electromagnetic wire treatment, and plasma treatment.

[0307] In one embodiment, the surface treatment is preferably a coating treatment with a polymer containing polar groups. This coating treatment can improve electrolyte impregnation and adhesion to the slurry dry product. Examples of polar groups include carboxylic acid groups, hydroxyl groups, sulfonic acid groups, and the like.

[0308] In one embodiment, the thickness (of the porous polyolefin resin substrate) is preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

[0309] (Plastic nonwoven fabric) Examples of plastic nonwoven fabrics include nonwoven fabrics composed solely of synthetic fibers.

[0310] 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, phenolic resins, melamine resins, furan resins, urea resins, aniline resins, unsaturated polyester resins, alkyd resins, fluorine resins, 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.

[0311] Examples of polyolefin resins include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymers, and olefin copolymers.

[0312] Examples of polyester resins include polyethylene terephthalate (PET) resins, polybutylene terephthalate (PBT) resins, polytrimethylene terephthalate (PPT) resins, polyethylene naphthalate (PEN) resins, polybutylene naphthalate resins, polyethylene isonaphthalate resins, and fully aromatic polyester resins.

[0313] Examples of acrylonitrile resins include polyacrylonitrile, copolymers of acrylonitrile and (meth)acrylic acid derivatives, vinyl acetate, etc.

[0314] Examples of polyamide resins include aliphatic polyamides, fully aromatic polyamides, and semi-aromatic polyamides.

[0315] Examples of aliphatic polyamides include nylon.

[0316] Examples of fully aromatic polyamides include poly-p-phenylene terephthalamide, poly-p-phenylene terephthalamide-3,4-diphenyl ether terephthalamide, and poly-m-phenylene isophthalamide.

[0317] "Semi-aromatic polyamide" refers to a polyimide in which part of the main chain of an aromatic polyamide is a fatty acid chain.

[0318] Plastic nonwoven fabric fibers may optionally include fibers other than synthetic resin fibers.

[0319] Other fibers besides synthetic resin fibers include, for example, solvent-spun cellulose, solvent-spun cellulose fibrils, regenerated cellulose, regenerated cellulose fibrils, natural cellulose fibers, natural cellulose fiber pulps, natural cellulose fiber fibrils, and inorganic fibers.

[0320] The mass % content (fibers other than synthetic fibers / nonwoven fabrics) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less.

[0321] Examples of fiber forms include single fibers and composite fibers.

[0322] "Single fiber" refers to a fiber made of a single resin. "Composite fiber" refers to a fiber made of two or more types of resins.

[0323] Examples of morphologies (composite fibers) include core-sheath type, eccentric type, side-by-side type, sea-island type, orange type, and multi-bimetal type.

[0324] In one embodiment, the average fiber diameter (plastic nonwoven fabric) is preferably 1 μm to 15 μm, and more preferably 1 μm to 10 μm.

[0325] "Average fiber diameter" refers to the average fiber diameter of 20 fibers randomly selected from scanning electron microscope images.

[0326] 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.

[0327] "Pore diameter" refers to the width of the gap between fibers. "Average pore diameter" refers to the average value of the pore diameters of 20 fibers randomly selected from scanning electron microscope images.

[0328] In one embodiment, the thickness (of the plastic nonwoven fabric) is preferably 5 μm to 25 μm, and more preferably 5 μm to 15 μm.

[0329] <Manufacturing Method (Energy Storage Device Separator)> Manufacturing methods (for energy storage device separators) include, for example, a coating step of coating a substrate with an energy storage device separator slurry, and a drying step of drying the coated energy storage device separator slurry.

[0330] (Coating process) Coating methods include, for example, coating methods, printing methods, transfer methods, and immersion methods.

[0331] Coating methods include, for example, blades, rods, reverse rolls, lips, dies, curtains, and air knives.

[0332] Printing methods include, for example, flexographic, screen printing, offset printing, gravure printing, and inkjet printing.

[0333] Examples of transfer methods include roll transfer and film transfer.

[0334] Immersion methods include, for example, dipping.

[0335] (drying process) Drying methods include, for example, air drying, irradiation drying, and vacuum drying.

[0336] Examples of air drying include hot air drying, warm air drying, and low-humidity air drying.

[0337] Irradiation drying methods include, for example, infrared irradiation drying, far-infrared irradiation drying, and electron beam irradiation drying.

[0338] The drying temperature is preferably 40°C to 90°C, and more preferably 50°C to 80°C.

[0339] The drying time is preferably 5 seconds to 3 minutes, and more preferably 15 seconds to 2 minutes.

[0340] The manufacturing method (for the energy storage device separator) may optionally include a pressing process.

[0341] Examples of pressing methods include die presses and roll presses.

[0342] The above-mentioned energy storage device separator can be used, for example, as a battery separator, a non-aqueous secondary battery separator, a lithium-ion battery separator, a sodium-ion battery separator, and the like.

[0343] [Energy storage device separator / electrode stack] This disclosure relates to an energy storage device separator / electrode laminate having a dried material of the above-mentioned energy storage device slurry on the active material side of the electrode.

[0344] The energy storage device separator / electrode laminate is obtained by applying the above-mentioned energy storage device slurry to the electrodes and drying it.

[0345] Examples of manufacturing methods (energy storage device separator / electrode laminate) include methods that include the following steps. (1) Step of applying an electrode material-containing slurry to the current collector. (2) Step of drying the slurry containing electrode material (3) Process of pressing the dried slurry containing electrode material. (4) Step of applying energy storage device separator slurry to the dried slurry containing electrode material. (5) Process of drying the energy storage device separator slurry

[0346] Examples of application methods, drying methods, and pressing methods include the methods described above.

[0347] Applications (energy storage device separator / electrode stacks) include, for example, battery separator / electrode stacks, battery separator / negative electrode stacks, battery separator / positive electrode stacks, non-aqueous secondary battery separator / electrode stacks, non-aqueous secondary battery separator / negative electrode stacks, non-aqueous secondary battery separator / positive electrode stacks, lithium-ion battery separator / electrode stacks, lithium-ion battery separator / negative electrode stacks, lithium-ion battery separator / positive electrode stacks, sodium-ion battery separator / electrode stacks, sodium-ion battery separator / negative electrode stacks, sodium-ion battery separator / positive electrode stacks, etc.

[0348] [Energy storage device electrolyte] This disclosure relates to an electrolyte for an energy storage device, which is a gel of the aqueous solution of the energy storage device described above.

[0349] The manufacturing method (electrolyte for energy storage devices) may include the following steps. (1) Drying process: The aqueous solution of the energy storage device described above is dried to obtain a dried product. (2) Swelling process: The above dried material is swelled in a dispersion medium.

[0350] Examples of drying conditions include those mentioned above.

[0351] Examples of dispersion media include electrolytes.

[0352] Examples of electrolytes include the solutions described later.

[0353] Applications (electrolytes for energy storage devices) include, for example, battery electrolytes, non-aqueous secondary battery electrolytes, lithium-ion battery electrolytes, sodium-ion battery electrolytes, and so on.

[0354] [Energy storage devices] This disclosure relates to an energy storage device.

[0355] In one embodiment, the energy storage device includes the energy storage device electrodes.

[0356] In one embodiment, the energy storage device includes the energy storage device separator.

[0357] In one embodiment, the energy storage device includes the energy storage device separator / electrode laminate.

[0358] In one embodiment, the energy storage device includes the energy storage device electrolyte.

[0359] (electrolyte) The energy storage device may optionally include an electrolyte. Examples of the electrolyte include a solution obtained by dissolving a supporting electrolyte in a non-aqueous solvent.

[0360] Non-aqueous solvents can be used alone or in combination of two or more.

[0361] Examples of non-aqueous solvents include linear carbonate solvents, cyclic carbonate solvents, linear ether solvents, cyclic ether solvents, linear ester solvents, cyclic ester solvents, and acetonitrile.

[0362] Examples of linear carbonate solvents include diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.

[0363] Examples of cyclic carbonate solvents include ethylene carbonate, propylene carbonate, and butylene carbonate.

[0364] Examples of chain-like ether solvents include 1,2-dimethoxyethane.

[0365] Examples of cyclic ether solvents include tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, and 1,3-dioxolane.

[0366] Examples of linear ester solvents include methyl formate, methyl acetate, and methyl propionate.

[0367] Examples of cyclic ester solvents include γ-butyrolactone and γ-valerolactone.

[0368] In one embodiment, the non-aqueous solvent is preferably a combination of a cyclic carbonate and a linear carbonate.

[0369] Supporting electrolytes can be used individually or in combination of two or more types.

[0370] 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, and (C2F5SO2)NLi. In one embodiment, the supporting electrolyte is preferably LiPF6, LiClO4, or CF3SO3Li.

[0371] In one embodiment, the non-aqueous electrolyte may optionally include a film-forming agent. The film-forming agent may be used alone or in combination of two or more.

[0372] Examples of film-forming agents include carbonates, alkenesulfides, sultones, and acid anhydrides.

[0373] Examples of carbonates include vinylene carbonate, vinylethylene carbonate, vinylethyl carbonate, methylphenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate.

[0374] Examples of alkene sulfides include ethylene sulfide and propylene sulfide.

[0375] Examples of sultones include 1,3-propanesultone and 1,4-butanesultone.

[0376] Examples of acid anhydrides include maleic anhydride and succinic anhydride.

[0377] In one embodiment, the mass% content (film-forming agent / electrolyte) is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

[0378] Examples of the forms (energy storage devices) include a cylinder type with sheet electrodes and separators arranged in a spiral, an inside-out cylinder type combining pellet electrodes and separators, and a coin type with stacked pellet electrodes and separators.

[0379] Examples of manufacturing methods (for energy storage devices) include the method described in Japanese Patent Publication No. 2013-089437.

[0380] Applications (energy storage devices) include, for example, batteries, non-aqueous secondary batteries, lithium-ion batteries, sodium-ion batteries, etc. [Examples]

[0381] The present invention will be specifically described below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only to the claims. Unless otherwise specified below, numerical values ​​such as parts and percentages are based on mass.

[0382] Example 1: Aqueous solution for energy storage devices In a reaction apparatus equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 833 g of deionized water, 19 g (0.21 mol) of 80% acrylic acid aqueous solution, 3.7 g (0.07 mol) of acrylonitrile, and 129 g (1.12 mol) of N-(2-hydroxyethyl)acrylamide were added. After removing oxygen from the reaction system with nitrogen gas, the temperature was raised to 55°C. 0.3 g of 2,2'-azobis-2-amidinopropane dihydrochloride and 3 g of deionized water were added as initiators, and the temperature was raised to 80°C for 3 hours. After the reaction was complete, 17.6 g (0.21 mol) of 48% sodium hydroxide aqueous solution was added, and deionized water was added to achieve a solid content concentration of 8% to obtain an aqueous solution for an energy storage device.

[0383] Unless otherwise specified, the following examples were performed in the same manner as above, except for the modifications shown in the table. The pH was adjusted using sodium hydroxide to achieve the pH values ​​listed in the table.

[0384] [Table 1] HEAAm: N-hydroxyethylacrylamide AA(Na): Total of acrylic acid and sodium acrylate AN: Acrylonitrile AM: Acrylamide I-AM: N-isopropylacrylamide HEA: Hydroxyethyl acrylate Examples 1-5 and Comparative Examples 1-3 were evaluated as negative electrode binders, Example 6 and Comparative Example 4 as positive electrode binders, and Example 7 and Comparative Example 5 as separator binders.

[0385] The measurement conditions (Type B viscosity) are as follows: Measurement temperature: 25℃ Type B Viscometer: Manufactured by Toki Sangyo Co., Ltd. Product name: "Type B Viscometer Model TVB-10" Viscosity 100 mPa·s to 10000 mPa·s: No. 3 rotor, rotation speed 12 rpm Viscosity over 10,000 mPa·s to 20,000 mPa·s: No. 3 rotor, rotation speed 6 rpm

[0386] The measurement conditions (pH) are as follows: Measuring instrument: Manufactured by Horiba, Ltd. Product name: "pH meter D-52" Measurement temperature: 25℃

[0387] <Dispersibility> The dispersibility of the energy storage device electrodes or separator slurries obtained as described below was visually evaluated. A: No foaming B: It foams up.

[0388] <Electrode flexibility> The electrodes obtained below were cut to a width of 20 mm and a length of 100 mm, wrapped around a 6 mm diameter Teflon® rod with the active material layer facing outwards, and the surface appearance of the active material layer was observed and evaluated according to the following criteria. A: There are absolutely no cracks or peeling in the active material layer bonded to the current collector. B: Cracks are visible in the active material layer bonded to the current collector, but no peeling is observed. C: Cracks and peeling are observed in the active material layer bonded to the current collector. Highly flexible electrodes are less prone to problems such as curling, cracking, and loss of active material during the electrode manufacturing process. On the other hand, electrodes with low flexibility are more likely to experience problems such as curling, cracking, and loss of active material during the electrode manufacturing process, which can easily reduce the discharge capacity retention rate.

[0389] <Adhesion> A test piece measuring 2 cm wide x 10 cm long was cut from the electrode or separator obtained below and fixed with the coated side facing upwards. Next, a 15 mm wide adhesive tape ("Sellotape®," manufactured by Nichiban Co., Ltd.) (as specified in JIS Z1522) was pressed onto the electrode layer surface of the test piece. Then, under 25°C conditions, the stress was measured when the adhesive tape was peeled off from one end of the test piece at a speed of 30 mm / min in a 180° direction using a tensile testing machine ("AGX-1kNNVD," manufactured by Shimadzu Corporation). The measurement was performed twice, converted to values ​​per 15 mm width, and the average value was calculated as the peel strength. (Negative electrode) A: 2N / m or more B: Less than 2N / m (positive electrode) A: 2N / m or more B: Less than 2N / m (Separator) A: 3N / m or more B: Less than 3N / m

[0390] <Operational evaluation (negative electrode of energy storage device)> (1-1) Manufacturing (negative electrode slurry for energy storage devices) Using a commercially available rotary-orbit mixer (product name "Awatori Rentaro", manufactured by Thinky Co., Ltd.), 5 parts by mass of the above-mentioned energy storage device aqueous solution (calculated on a non-volatile content basis) and 95 parts by mass of natural graphite (manufactured by Ito Graphite Industry Co., Ltd., product name "Z-5F") were mixed in a container specifically for the mixer. Ion-exchanged water was then added to achieve a solid content concentration of 40%, and the container was set in the mixer. Next, the mixture was kneaded at 2000 rpm for 10 minutes, followed by degassing for 1 minute to obtain an energy storage device anode slurry.

[0391] (1-2) Manufacturing (negative electrode of energy storage device) The negative electrode slurry of the energy storage device was uniformly applied to the surface of a current collector made of copper foil using the doctor blade method so that the film thickness after drying was 80 μm. After drying at 80°C for 30 minutes, the negative electrode was heat-treated at 100°C for 120 minutes. Subsequently, the negative electrode was pressed using a roll press machine to obtain the final negative electrode.

[0392] (1-3) Manufacturing (energy storage devices) In an argon-purged glove box, the negative electrode described above was punched out to a diameter of 16 mm and placed on a two-electrode coin cell (manufactured by Hosen Co., Ltd., product name "HS Flat Cell"). Next, a separator made of a porous polypropylene membrane punched out to a diameter of 24 mm (manufactured by CS TECH CO., LTD, product name "Selion P2010") was placed on top, and then 500 μL of electrolyte was injected to prevent air from entering. Finally, a commercially available metallic lithium foil punched out to 16 mm was placed on top, and the outer body of the two-electrode coin cell was closed with screws to seal it, thereby assembling the energy storage device (lithium half cell). The electrolyte used here was a solution of LiPF6 dissolved at a concentration of 1 mol / L in a solvent of ethylene carbonate / dimethyl carbonate = 3 / 7 (volume ratio).

[0393] The energy storage device having the negative electrode described above functioned without any problems.

[0394] <Operational evaluation (positive electrode of energy storage device)> (2-1) Manufacturing (Positive electrode slurry for energy storage devices) Using a commercially available rotary-orbit mixer (product name "Awatori Rentaro", manufactured by Thinky Co., Ltd.), 3 parts by mass of the above-mentioned energy storage device aqueous solution (based on solid content), 91 parts of lithium cobalt oxide LCO (LiCoO2, manufactured by Nippon Chemical Industrial Co., Ltd., product name "Cellseed C-5H") as the positive electrode active material, and 6 parts of acetylene black were mixed in a container specifically for the mixer. Ion-exchanged water was added to the mixture to a non-volatile content concentration of 50%, and the container was set in the mixer. Next, the mixture was kneaded at 2000 rpm for 10 minutes, followed by degassing for 1 minute to obtain the energy storage device positive electrode slurry.

[0395] (2-2) Manufacturing (Positive electrode of energy storage device) The positive electrode slurry of the energy storage device was uniformly applied to the surface of a current collector made of aluminum foil using the doctor blade method so that the film thickness after drying was 100 μm. After drying at 80°C for 30 minutes, the positive electrode was obtained by heat treatment at 150°C / vacuum for 120 minutes. Subsequently, the positive electrode was obtained by press processing using a roll press machine.

[0396] (2-3) Manufacturing (energy storage devices) In an argon-purged glove box, the positive electrode described above was punched out to a diameter of 16 mm and placed on a two-electrode coin cell (manufactured by Hosen Co., Ltd., product name "HS Flat Cell"). Next, a separator made of a porous polypropylene membrane punched out to a diameter of 24 mm (manufactured by CS TECH CO., LTD, product name "Selion P2010") was placed on top, and then 500 μL of electrolyte was injected to prevent air from entering. Finally, a commercially available metallic lithium foil punched out to 16 mm was placed on top, and the outer body of the two-electrode coin cell was closed with screws to seal it, thereby assembling the energy storage device (lithium half cell). The electrolyte used here was a solution of LiPF6 dissolved at a concentration of 1 mol / L in a solvent of ethylene carbonate / dimethyl carbonate = 3 / 7 (volume ratio).

[0397] The energy storage device having the above-mentioned positive electrode functioned without any problems.

[0398] <Operational evaluation (energy storage device separator)> (3-1) Manufacturing (Energy storage device separator slurry) Five parts by mass of the above energy storage device aqueous solution (based on solid content) and 113 parts by mass of water were stirred and mixed. 100 parts by mass of boehmite (average particle size 0.8 μm) were added as non-conductive particles, and the mixture was dispersed and stirred in a homogenizer (IKA T25 digital ULTRA-TURRAX) at 15,000 rpm for 60 minutes. Deionized water was then added to adjust the viscosity, and an energy storage device separator slurry was produced.

[0399] (3-2) Manufacturing (Separator): Lamination of separator slurry layer (coating layer) A single-layer polyethylene separator substrate (PE substrate) with a width of 250 mm, a length of 200 mm, and a thickness of 6 μm, manufactured by a wet process, was prepared. The above energy storage device separator slurry was coated onto one surface of the separator using a gravure coater so that the thickness after drying would be 3.0 μm, and then dried to obtain an energy storage device separator.

[0400] (3-3) Manufacturing (Energy Storage Devices) (1-3) In the manufacturing (energy storage device), the energy storage device was manufactured using the same method as above, except that the separator was replaced with the one manufactured above.

[0401] The energy storage device having the above-mentioned energy storage device separator functioned without any problems.

Claims

1. Aqueous solution for an energy storage device, The aforementioned aqueous solution of the energy storage device contains a water-soluble polymer, The aforementioned water-soluble polymer is an aqueous solution for an energy storage device, comprising hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units.

2. Energy storage device slurry, The energy storage device slurry comprises a water-soluble polymer and water. The aforementioned water-soluble polymer is a slurry for energy storage devices, comprising hydroxyl group-containing (meth)acrylamide units and α,β-unsaturated nitrile units.

3. A slurry for an energy storage device according to claim 2, comprising an electrode active material.

4. The energy storage device slurry according to claim 2, comprising non-conductive particles.

5. An electrode for a power storage device, having a dried material of the power storage device slurry described in claim 2 or 3 on a current collector.

6. A storage device separator having a dried product of the storage device slurry described in claim 2 or 4 on a substrate.

7. A storage device separator / electrode laminate having a dried product of the storage device slurry according to claim 2 or 4 on the active material side of the electrode.

8. An electrolyte for an energy storage device, which is a gelled form of the aqueous solution of the energy storage device described in claim 1.

9. A power storage device comprising the power storage device electrode described in claim 5.

10. A storage device comprising the energy storage device separator described in claim 6.

11. A storage device comprising the energy storage device separator / electrode laminate described in claim 7.

12. A power storage device comprising the power storage device electrolyte described in claim 8.

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