CN109935834A - Lithium ion battery heat cross-linking binder aqueous solution, electrode slurry and its manufacturing method, lithium ion battery electrode and battery - Google Patents

Lithium ion battery heat cross-linking binder aqueous solution, electrode slurry and its manufacturing method, lithium ion battery electrode and battery Download PDF

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CN109935834A
CN109935834A CN201811541472.2A CN201811541472A CN109935834A CN 109935834 A CN109935834 A CN 109935834A CN 201811541472 A CN201811541472 A CN 201811541472A CN 109935834 A CN109935834 A CN 109935834A
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mass
lithium ion
methyl
ion battery
moles
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CN109935834B (en
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池谷克彦
尾崎真仁
合田英生
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract

[technical problem] provides lithium ion battery heat cross-linking binder aqueous solution, lithium ion battery electrode slurry and its manufacturing method, lithium ion battery electrode and lithium ion battery.[technological means] this application provides lithium ion battery heat cross-linking binder aqueous solutions, the lithium ion battery heat cross-linking binder aqueous solution contains water-soluble poly (methyl) acrylamide (A) of hydroxyl, the solidfied material gelling point rate of water-soluble poly (methyl) acrylamide (A) of the hydroxyl is 20% or more and is the polymer of following monomer groups: relative to 100 moles of % of monomer group, the monomer group contains the compound (a) containing (methyl) acrylamido of 30 moles of %-95 moles of %, (methyl) acrylate (b) of the hydroxyl of 5 moles of %-50 moles of %.

Description

Lithium ion battery heat cross-linking binder aqueous solution, electrode slurry and its manufacturer Method, lithium ion battery electrode and battery
Technical field
This application involves lithium ion battery heat cross-linking binder aqueous solution, lithium ion battery electrode slurry and its systems Make method, lithium ion battery electrode and lithium ion battery.
Background technique
Lithium ion battery is had small-sized, light weight, energy density high and can be had been used for the characteristic of repeated charge Extensive purposes.Therefore, in recent years, for the purpose of the further high performance of lithium ion battery, just in batteries such as Electrodes The improvement of component.
The anode and cathode of lithium ion battery are all manufactured by following methods: electrode active material and adhesive resin are existed Disperse the slurry to be formed in solvent and carry out double spread in collector (such as metal foil), solvent seasoning is removed to form electrode After layer, it is used into the compression formings such as roll squeezer.
Lithium ion battery mainly contains active material, adhesive and solvent with slurry.So far, adhesive is usually used As the adhesive resin being dissolved in the organic solvents such as n-methyl-2-pyrrolidone (NMP) Kynoar (PVdF) and The styrene-butadiene type lotion (SBR latex) of the adhesive resin of particle shape resin as aqueous dispersion.
In recent years, in lithium ion battery electrode, from the viewpoint of improving battery capacity, various electricity are proposed Pole active material.However, depending on electrode active material, expansion and contraction are easy to produce with charge and discharge.Therefore, with charge and discharge Capacitor is also easy to produce expansion and the lithium ion battery electrode of contraction can occur volume change (rebound due to the initial stage of repeated charge Property), it is easily reduced using electrical characteristics such as the cycle characteristics of lithium ion battery of lithium ion battery electrode.
Then, in the art, studying and attempting to use adhesive resin to solve above-mentioned technical problem, such as proposing It is obtained by using the polyacrylamide (patent document 1 and patent document 2) of the adhesive as water-soluble resin good Charge-discharge characteristic.In addition, proposing expansion and contraction with active material charge and discharge by as adhesive tree Crosslinking agent is added in the particle shape resin of rouge to inhibit to expand (patent document 3).Crosslinking agent is usually coated with by paste compound Reaction is crosslinked in drying steps after collector, forms crosslinking in grade between the particle of particle shape resin.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-118908 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2015-106488 bulletin
Patent document 3: International Publication No. 2015/098507
Summary of the invention
Technical problems to be solved by the inivention
However, from the viewpoint of ensuring the dissolubility for water, the polyacrylamide of patent document 1 and patent document 2 Amine cannot reach the molecular weight of adhesive resin degree not soluble in water.As a result, there are caused by active mass expansion To the technical problem of elastic patience deficiency.
According to circumstances, the crosslinking agent recorded in patent document 3 and with not exhibiting effect a large amount of addition sometimes yet. In this case, when largely adding crosslinking agent to show the effect (such as patience to rebound) of crosslinking agent, due to There are adherence of the electrode active material layer to collector to reduce instead, it is desired as high-temperature cycle to obtain The case where effect, therefore there are also further rooms for improvement.
In turn, the adhesive composition containing crosslinking agent and particle shape binder is after preparation into the storage period used Deterioration, can not play desired performance sometimes.For example, in storage period after preparation, it sometimes appear that carrying out unexpected Crosslinking, phenomena such as viscosity rises, the reactivity of crosslinking agent reduces the case where, therefore there are also further room for improvement.
Therefore, the technical problem to be solved in the present invention is that, providing can assign lithium ion battery good electrode sticking Property and the lithium ion battery slurry of battery behaviors such as resistance to rebound and the lithium ion battery of above-mentioned slurry can be manufactured handed over heat Connection property binder aqueous solution.
Solve the technological means of technical problem
It is in order to solve the above-mentioned technical problem present inventor concentrates on studies as a result, it has been found that, by using with defined insatiable hunger With monomer as constituent and to have poly- (methyl) acrylamide of regulation physical property to make bonding as main component Agent aqueous solution can solve above-mentioned technical problem, so as to complete the present invention.
Following items are provided by the application.
(project 1)
Lithium ion battery heat cross-linking binder aqueous solution, lithium ion battery heat cross-linking binder aqueous solution Water-soluble poly (methyl) acrylamide (A) containing hydroxyl,
The solidfied material gelling point rate (ゲ Le divides rate) of water-soluble poly (methyl) acrylamide (A) of the hydroxyl is 20% Above and be following monomer groups polymer: relative to 100 moles of % of monomer group, the monomer group contains 30 moles of %-95 The compound (a) containing (methyl) acrylamido of mole %, 5 moles of %-50 moles of % hydroxyl (methyl) acrylic acid Ester (b).
(project 2)
Lithium ion battery heat cross-linking binder aqueous solution as described in above-mentioned the project, wherein (first of the hydroxyl Base) acrylate (b) by the following general formula (1) indicate:
General formula (1):
[changing 4]
In formula, R1Indicate hydrogen atom or methyl；
R2Indicate the alkylidene oxide of substituted or unsubstituted carbon number 1-5,
The polyoxyalkylene indicated by general formula (2),
General formula (2):
[changing 5]
In formula, integer of the q for 1-3, the integer that n is 1 or more,
[changing 6]
Or their combination.
(project 3)
Contain the lithium ion battery as described in any one of above-mentioned project heat cross-linking binder aqueous solution and electrode active The lithium ion battery electrode slurry of property substance (B).
(project 4)
Lithium ion battery electrode slurry as described in above-mentioned project, wherein relative to the electrode active material (B) 100 mass %, the water-soluble poly (methyl) of the hydroxyl contained in the lithium ion battery heat cross-linking binder aqueous solution Acrylamide (A) is 1 mass %-15 mass %.
(project 5)
Lithium ion battery electrode slurry as described in any one of above-mentioned project, wherein the electrode active material (B) The silicon or silica of carbon-coating covering containing 5 mass % or more.
(project 6)
The manufacturing method of lithium ion battery electrode slurry as described in any one of above-mentioned project, the method includes will The step of water-soluble poly (methyl) acrylamide (A) and electrode active material (B) mixing of hydroxyl, wherein
The solidfied material gelling point rate of water-soluble poly (methyl) acrylamide (A) of the hydroxyl is 20% or more and is The polymer of following monomer groups: relative to 100 moles of % of monomer group, the monomer group contains containing for 30 moles of %-95 moles of % The compound (a) of (methyl) acrylamido, 5 moles of %-50 moles of % hydroxyl (methyl) acrylate (b).
(project 7)
By the way that the lithium ion battery electrode slurry as described in any one of above-mentioned project to be coated on the current collector and make Lithium ion battery electrode obtained from it is dried.
(project 8)
Lithium ion battery electrode as described in above-mentioned project, wherein the collector is copper foil.
(project 9)
Lithium ion battery electrode as described in any one of above-mentioned project, wherein the lithium ion battery is logical with electrode The drying steps crossed at 80 DEG C -200 DEG C obtain.
(project 10)
Lithium ion battery comprising the lithium ion battery electrode as described in any one of above-mentioned project.
Beneficial effect
Lithium ion battery electrode slurry of the invention is due to water-soluble poly (methyl) acrylamide containing hydroxyl Therefore excellent storage stability (A),.Further, since having heat cross-linking can by using the electrode obtained by above-mentioned slurry To obtain the lithium ion battery that resistance to resilience improves.
Lithium ion battery of the invention is using water-soluble poly (methyl) acrylamide (A) containing hydroxyl with electrode What above-mentioned slurry obtained, therefore even if it is excellent also to provide resistance to resilience in the case where carrying out heat cross-linking, improving battery capacity Lithium ion battery.
Lithium ion battery of the invention is since equipped with electrode of the present invention, resistance to resilience is excellent.
Specific embodiment
In the full text of the application, the ranges of the numerical value such as value, content of each physical property can be appropriate (such as from following each Selected in the value of upper and lower bound documented by project) setting.Specifically, for numerical value α, the upper limit of numerical value α be, for example, A1, A2, A3 etc., the lower limit of numerical value α are, for example, B1, B2, B3 etc., in the case, the range of numerical value α be, for example, A1 or less, A2 with Under, A3 or less, B1 or more, B2 or more, B3 or more, A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3~ B1, A3~B2, A3~B3 etc..
[1. lithium ion batteries with heat cross-linking binder aqueous solution (also referred to as aqueous solution (1))]
This application provides lithium ion battery heat cross-linking binder aqueous solution, the lithium ion battery heat cross-linking Binder aqueous solution contains water-soluble poly (methyl) acrylamide (A) of hydroxyl, the water-soluble poly (methyl) of the hydroxyl The solidfied material gelling point rate of acrylamide (A) is 20% or more and is the polymer of following monomer groups: relative to monomer group 100 Mole %, the monomer group contain the compound (a) containing (methyl) acrylamido of 30 moles of %-95 moles of %, 5 rub (methyl) acrylate (b) of the hydroxyl of your %-50 moles of %.
<compound (a) (hereinafter also referred to (a) ingredient) for containing (methyl) acrylamido>
In this application, " compound for containing (methyl) acrylamido " refers to the chemical combination with (methyl) acrylamido Object.Compound containing (methyl) acrylamido can not be particularly restrictedly using various well known compounds, can be independent It uses, also can be used together two or more.
In this application, " (methyl) acrylic acid " refers to " selects from the group being made of acrylic acid and methacrylic acid It is at least one ".Similarly, " (methyl) acrylate " refers to and " selects from the group being made of acrylate and methacrylate At least one selected ".Meanwhile " (methyl) acryloyl group " refers to " from the group being made of acryloyl group and methylacryloyl At least one of selection ".
In one embodiment, the compound containing (methyl) acrylamido is indicated by following structural formula:
[changing 7]
In formula, R1It is hydrogen or methyl, R2And R3It is separately hydrogen, substituted or unsubstituted alkyl, acetyl group or sulfonic acid Base or R2And R3For the group that ring structure is collectively formed, R4And R5It is separately hydrogen, substituted or unsubstituted alkyl, carboxylic Base, hydroxyl, amino (- NRaRb(RaAnd RbBe separately hydrogen or substituted or unsubstituted alkyl) (the same below)), acetyl Base, sulfonic group.The substituent group for replacing alkyl is, for example, hydroxyl, amino, acetyl group, sulfonic group etc..Meanwhile R2And R3It is collectively formed The group of ring structure is, for example, morpholinyl (モ Le ホ リ Le) etc..
Alkyl is, for example: straight chained alkyl, branched alkyl, naphthenic base etc..
Straight chained alkyl is by general formula-CnH2n+1(n is 1 or more integer) indicates.Straight chained alkyl is, for example: methyl, ethyl, third Base, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl (n- デ カ メ チ Le base) etc..
Branched alkyl is at least one hydrogen of straight chained alkyl by alkyl-substituted group.Branched alkyl is, for example: diethyl Amyl, trimethyl butyl, tri-methyl-amyl, trimethyl etc..
Naphthenic base is, for example: monocyclic cycloalkyl, bridged ring naphthenic base, condensed ring naphthenic base etc..
In this application, monocycle refer to it is being formed by the covalent bond of carbon, in the internal cyclic structure for not having bridging structure. Meanwhile condensed ring refers to that more than two monocycles share two atoms (that is, each ring only shares (condensed) a line from each other) Cyclic structure.Bridged ring refers to that more than two monocycles share the cyclic structure of 3 or more atoms.
Monocyclic cycloalkyl is, for example: cyclopenta, cyclohexyl, suberyl, cyclodecyl, 3,5,5- trimethylcyclohexyl etc..
Bridged ring naphthenic base is, for example: tricyclodecyl, adamantyl, norborny etc..
Condensed ring naphthenic base is, for example: bicyclodecyl etc..
The above-mentioned compound (a) containing (methyl) acrylamido is, for example: (methyl) acrylamide, N- isopropyl (methyl) Acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dimethylaminopropyl (methyl) acrylamide, N- methylol (methyl) acrylamide, diacetone (methyl) acrylamide, maleic acid, (methyl) Acrylamide tert-butyl sulfonic acid, (methyl) acryloyl morpholine, ethoxy (methyl) acrylamide and their salt etc.；Above-mentioned salt example It is in this way: dimethylaminopropyl (methyl) acrylamide chloro methane quaternary salt (4 grades of salt of salt メ チ Le), dimethyl aminoethyl (methyl) acrylate benzyl chloride quaternary salt (4 salt of ベ Application ジ Le Network ロ ラ イ De) etc..Wherein, if using (methyl) acryloyl If amine (especially acrylamide), then high water solubility, point with the interaction height of electrode active material, slurry can be made Dissipate the adhesive that the associativity of electrode active material from each other is high in property and electrode interior.
Relative to 100 moles of % of above-mentioned monomer group, the upper limit of the content of the compound containing (methyl) acrylamido is for example It is: 95 moles of %, 90 moles of %, 80 moles of %, 70 moles of %, 60 moles of %, 59 moles of %, 50 moles of %, 40 moles of %, 35 Mole % etc.；Lower limit is, for example: 90 moles of %, 80 moles of %, 70 moles of %, 60 moles of %, 59 moles of %, 50 moles of %, 40 Mole %, 35 moles of %, 30 moles of % etc..In one embodiment, the lower limit of above-mentioned content is preferably 30 moles of % or more. In addition, above-mentioned content ranges preferably from 30 moles of %-95 moles of %, more preferably 30 moles of %-93 moles of %, particularly preferably For 30 moles of %-90 moles of %.By being set as above-mentioned content, the dispersibility of electrode active material and filler becomes well, can Uniform electrode active material layer and protective film are made, therefore fault of construction disappears, and shows good charge-discharge characteristic；Further Ground, since the inoxidizability of polymer becomes good, it is believed that deterioration when high voltage can be inhibited, show good charge and discharge Wear properties, but be not meant to limit the invention to this.
Relative to above-mentioned 100 mass % of monomer group, the upper limit of the content of the compound containing (methyl) acrylamido is for example It is: 80 mass %, 75 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 25 mass % etc.； Lower limit is, for example: 75 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 25 mass %, 20 Quality % etc..In one embodiment, relative to above-mentioned 100 mass % of monomer group, contain the chemical combination of (methyl) acrylamido The content of object is preferably 20 mass %-80 mass %.
<(methyl) acrylate (b) (also referred to as (b) ingredient) of hydroxyl>
In this application, " (methyl) acrylate of hydroxyl " refers to hydroxyl and (methyl) acrylate-based change Close object.(methyl) acrylate of hydroxyl can not individually be made particularly restrictedly using various well known substances With also can be used together two or more.
(methyl) acrylate (b) of hydroxyl is, for example: (methyl) acrylate, (methyl) acrylic acid hydroxyl second Ester, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl, 3- hydroxyl -1- adamantyl (methyl) acrylate, 1,4- Cyclohexanedimethanol list (methyl) acrylate, glycerol list (methyl) acrylate, glycerol two (methyl) acrylate, 2- hydroxyl Mono- (methyl) propylene of base -3- phenoxy propyl (methyl) acrylate, pentaerythrite three (methyl) acrylate, polyethylene glycol - Mono- (methyl) acrylate of acid esters, polypropylene glycol-, mono- (methyl) acrylate of polyethylene glycol-propylene glycol-etc..
Wherein, (methyl) acrylate (b) (especially (methyl) acrylic acid hydroxyl second of the hydroxyl indicated by general formula (1) Mono- (methyl) acrylate of ester, polyethylene glycol -) it is easy to get, it can be with the water-soluble of the high hydroxyl of synthesizing water-solubility using them Property poly- (methyl) acrylamide (A), therefore preferably.
General formula (1):
[changing 8]
In formula, R1Indicate hydrogen atom or methyl；
R2Indicate the alkylidene oxide of substituted or unsubstituted carbon number 1-5,
The polyoxyalkylene indicated by general formula (2),
General formula (2):
[changing 9]
In formula, integer of the q for 1-3, the integer that n is 1 or more,
[changing 10]
Or their combination.
Alkylidene is, for example: straight-chain alkyl-sub, branched alkylidene, cycloalkylidene etc..
Straight-chain alkyl-sub can be by general formula-(CH2)n(integer that n is 1 or more) indicates.Straight-chain alkyl-sub is, for example: methylene Base, ethylidene, propylidene, positive butylidene and positive pentylidene etc..
Branched alkylidene is at least one hydrogen of straight-chain alkyl-sub by alkyl-substituted group.Branched alkylidene is, for example: Methylmethylene, ethyl methylene, propylmethylene, butyl methylene, methyl ethylidene, ethylethylene residue, propyl ethylidene, Methyl propylene, 2- ethylpropylene, dimethylpropylidene, methylbutylene etc..
Cycloalkylidene is, for example: monocycle cycloalkylidene, bridged ring cycloalkylidene, condensed ring cycloalkylidene etc..
Monocycle cycloalkylidene is, for example, cyclopentylene etc..
In one embodiment, relative to 100 moles of % of above-mentioned monomer group, (methyl) acrylate (b) of hydroxyl The upper limit of content be, for example: 50 moles of %, 48 moles of %, 45 moles of %, 40 moles of %, 30 moles of %, 20 moles of %, 10 are rubbed Your %, 5.5 moles of %, 5.1 moles of % etc.；Lower limit is, for example: 48 moles of %, 45 moles of %, 40 moles of %, 30 moles of %, 20 Mole %, 10 moles of %, 5.5 moles of %, 5.1 moles of %, 5 moles of % etc..In one embodiment, above-mentioned content is preferably 5 moles of %-50 moles of %, more preferably 5.5 moles of %-48 moles of %.By (methyl) acrylate (b) phase for making hydroxyl Content for above-mentioned 100 moles of % of monomer group is above range, and heat cross-linking sufficiently carries out, it is believed that can ensure heat cross-linking Resistance to elastic effect when charge and discharge is shown while the storage-stable of binder aqueous solution or heat cross-linking electrode slurry Fruit, but be not meant to limit the invention to this.
Relative to above-mentioned 100 mass % of monomer group, the upper limit of the content of (methyl) acrylate (b) of hydroxyl is for example It is: 70 mass %, 65 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 15 mass % etc.； Lower limit is, for example, 65 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 15 mass %, 10 matter Measure % etc..In one embodiment, relative to above-mentioned 100 mass % of monomer group, (methyl) acrylate (b) of hydroxyl Content is preferably 10 mass %-70 mass %.
<monomer (also referred to as (c) ingredient) other than (a) ingredient, (b) ingredient>
In above-mentioned monomer group, as long as not reducing the desired effect of the present invention, can be used (a) ingredient, (b) ingredient with Outer monomer ((c) ingredient).(c) ingredient can be used alone, and also can be used together two or more.(c) ingredient is, for example: containing insatiable hunger With the monomer of the acid groups such as carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid；The not esters of unsaturated carboxylic acids of hydroxyl；α, β-unsaturation Nitrile compound；Conjugated diene compound；Aromatic vinyl compound etc..
Unsaturated carboxylic acid is, for example: acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and it Salt etc..
The content of unsaturated carboxylic acid is not particularly restricted, if it is considered that reacting with above-mentioned (b) ingredient, relative to monomer Group 100 moles of %, preferably less than 45 moles of % (are, for example, less than 42 moles of %, less than 41 moles %, less than 40 moles %, small In 30 moles of %, less than 20 moles %, less than 19 moles %, less than 15 moles %, less than 10 moles %, less than 5 moles %, small In 1 mole of %, 0 mole of %).
In one embodiment, relative to above-mentioned 100 mass % of monomer group, the content of unsaturated carboxylic acid is preferably less than 45 mass % (be, for example, less than 42 mass %, less than 41 mass %, less than 40 mass %, less than 30 mass %, less than 20 matter Measure %, less than 19 mass %, less than 15 mass %, less than 10 mass %, less than 5 mass %, less than 1 mass %, 0 mass %).
Unsaturated sulfonic acid is, for example: the α such as vinyl sulfonic acid, styrene sulfonic acid, (methyl) acrylic sulfonic acid, β-olefinic is not It is saturated sulfonic acid；(methyl) acrylamide tert-butyl sulfonic acid, 2- (methyl) acrylamide -2- methyl propane sulfonic acid, 2- (methyl) third Acrylamide -2- hydroxypropanesulfonic acid, 3- sulfonic group propane (methyl) acrylate, double-(3- sulfonic group propyl) itaconate with And their salt etc..The content of unsaturated sulfonic acid is not particularly restricted, if it is considered that reacting with above-mentioned (b) ingredient, relatively In 100 moles of % of monomer group, the upper limit of the content of unsaturated sulfonic acid is, for example: 40 moles of %, 30 moles of %, 20 moles of %, 19 Mole %, 15 moles of %, 10 moles of %, 5 moles of %, 1 mole of %, 0.5 mole of %, 0.1 mole of %, 0.05 mole of %, 0.02 Mole %, 0.01 mole of % etc.；Lower limit is, for example: 30 moles of %, 20 moles of %, 19 moles of %, 15 moles of %, 10 moles of %, 5 Mole %, 1 mole of %, 0.5 mole of %, 0.1 mole of %, 0.05 mole of %, 0.02 mole of %, 0.01 mole of %, 0 mole of % Deng.
Relative to 100 mass % of monomer group, the upper limit of the content of unsaturated sulfonic acid is, for example: 40 mass %, 30 mass %, 20 mass %, 19 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 Quality %, 0.02 mass %, 0.01 mass % etc.；Lower limit is, for example: 30 mass %, 20 mass %, 19 mass %, 15 matter Measure %, 10 mass %, 5 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.05 mass %, 0.02 mass %, 0.01 Quality %, 0 mass % etc..
Unsaturated phosphorus acid monomer is, for example: vinyl phosphoric acid, vinyl phosphate, bis- ((methyl) acryloyl-oxyethyls) Phosphate, diphenyl -2- (methyl) acryloyl-oxyethyl phosphate, dibutyl -2- (methyl) acryloyl-oxyethyl phosphoric acid Ester, dioctyl -2- (methyl) acryloyl-oxyethyl phosphate, monomethyl -2- (methyl) acryloyl-oxyethyl phosphate, 3- (methyl) acryloxy -2- hydroxy propane phosphoric acid and their salt etc..The content of unsaturated phosphoric acid is not particularly restricted, If it is considered that being reacted with above-mentioned (b) ingredient, relative to 100 moles of % of monomer group, preferably less than 40 moles of % (it is, for example, less than 30 moles of %, less than 20 moles %, less than 19 moles %, less than 15 moles %, less than 10 moles %, less than 5 moles %, it is less than 1 mole of %, 0 mole of %).
Relative to 100 mass % of monomer group, the content of unsaturated phosphorus acid monomer is preferably less than 40 mass % and (is, for example, less than 30 mass %, less than 20 mass %, less than 19 mass %, less than 15 mass %, less than 10 mass %, less than 5 mass %, be less than 1 mass %, 0 mass %).
In one embodiment, relative to 100 moles of % of monomer group, contain unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturation The content of the monomer of the acid groups such as phosphoric acid is preferably less than 40 moles of % and (is, for example, less than 30 moles of %, less than 20 moles %, is less than 19 moles of %, less than 15 moles %, less than 10 moles %, less than 5 moles %, less than 1 mole %, 0 mole of %).
In one embodiment, relative to 100 mass % of monomer group, contain unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturation The content of the monomer of the acid groups such as phosphoric acid be preferably less than 40 mass % (be, for example, less than 30 mass %, less than 20 mass %, be less than 19 mass %, less than 15 mass %, less than 10 mass %, less than 5 mass %, less than 1 mass %, 0 mass %).
The esters of unsaturated carboxylic acids of hydroxyl is not preferably (methyl) acrylate of not hydroxyl.Not (methyl) of hydroxyl Acrylate is, for example: not straight chain (methyl) acrylate of hydroxyl, not branch (methyl) acrylate of hydroxyl, be free of Substitution (methyl) acrylate of alicyclic ring (methyl) acrylate of hydroxyl, not hydroxyl etc..
Straight chain (methyl) acrylate of hydroxyl is not, for example: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) Hexyl 2-propenoate, (first Base) n-octyl, (methyl) nonyl acrylate, (methyl) decyl acrylate etc..
Branch (methyl) acrylate of hydroxyl is not, for example: (methyl) isopropyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) isoamyl acrylate, (methyl) 2-EHA etc..
Alicyclic ring (methyl) acrylate of hydroxyl is not, for example, (methyl) cyclohexyl acrylate etc..
The content of the esters of unsaturated carboxylic acids of hydroxyl is not particularly restricted, by using the unsaturated carboxylic of not hydroxyl Acid esters can inhibit to be reduced by the glass transition temperature of water-soluble poly (methyl) acrylamide (A) of hydroxyl of the invention Caused by electrode curling.On the other hand, if it is considered that the resistance to resilience of lithium ion battery of the invention, relative to monomer group 100 moles of %, it (is, for example, less than 30 moles of %, small that the content of the esters of unsaturated carboxylic acids of hydroxyl, which is not preferably less than 40 moles of %, It rubs in 20 moles of %, less than 19 moles %, less than 15 moles %, less than 10 moles %, less than 5 moles %, less than 1 mole %, 0 You are %).
In one embodiment, relative to 100 mass % of monomer group, the content of the esters of unsaturated carboxylic acids of hydroxyl is not excellent Be selected as less than 40 mass % (be, for example, less than 30 mass %, less than 20 mass %, less than 19 mass %, less than 15 mass %, be less than 10 mass %, less than 5 mass %, less than 1 mass %, 0 mass %).
For electrode of the invention is assigned with the purpose of flexibility, α, alpha, beta-unsaturated nitriles compound can be properly used. 'alpha ', ' bela '-unsaturated nitrile compound is, for example: (methyl) acrylonitrile, α-chlorine (methyl) acrylonitrile, α-ethyl (methyl) acrylonitrile, partially Two acrylonitriles (シ ア Application ビ ニ リ デ Application) etc..Wherein, preferred (methyl) acrylonitrile, particularly preferred acrylonitrile.α, β-unsaturation The content of nitrile compound is not particularly restricted, relative to 100 moles of % of monomer group, preferably less than 40 moles of % (such as it is small In 30 moles of %, less than 20 moles %, less than 19 moles %, less than 15 moles %, less than 10 moles %, less than 5 moles %, small In 1 mole of %, 0 mole of %).By making relative to 100 moles of % of monomer group, the content of α, alpha, beta-unsaturated nitriles compound are less than 40 moles of %, keep hydroxyl water-soluble poly (methyl) acrylamide (A) to water it is deliquescent simultaneously, above-mentioned slurry Electrode layer becomes uniformly, and playing above-mentioned flexibility will become easy.
In one embodiment, relative to 100 mass % of monomer group, the content of α, alpha, beta-unsaturated nitriles compound are preferably Less than 40 mass % (be, for example, less than 30 mass %, less than 20 mass %, less than 19 mass %, less than 15 mass %, less than 10 matter Measure %, less than 5 mass %, less than 1 mass %, 0 mass %).
Conjugated diene compound is, for example: 1,3- butadiene, 2- methyl-1,3- butadiene, 2,3- dimethyl -1,3- fourth two The chloro- 1,3- butadiene of alkene, 2-, substituted straight chain conjugation pentadiene, the conjugation hexadiene for replacing and there is side chain etc..Conjugated diene The content of compound is not particularly restricted, from the viewpoint of the resistance to resilience of lithium ion battery of the present invention, upper It states in 100 moles of % of monomer group, preferably less than 10 moles of %, more preferably 0 mole of %.
In one embodiment, relative to 100 mass % of monomer group, the content of conjugated diene compound is preferably less than 10 mass %, more preferably 0 mass %.
In addition, aromatic vinyl compound is, for example: styrene, α-methylstyrene, p-methylstyrene, vinyl first Benzene, chlorostyrene, divinylbenzene etc..The content of aromatic vinyl compound is not particularly restricted, from of the present invention From the viewpoint of the resistance to resilience of lithium ion battery, in 100 moles of % of above-mentioned monomer group, preferably less than 10 moles of %, more Preferably 0 mole of %.
In one embodiment, relative to 100 mass % of monomer group, the content of aromatic vinyl compound is preferably small In 10 mass %, more preferably 0 mass %.
Above-mentioned monomer, esters of unsaturated carboxylic acids, α containing acid groups such as unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, (c) ingredient other than alpha, beta-unsaturated nitriles compound, conjugated diene compound, aromatic vinyl compound institute's accounting in monomer group Example relative to 100 moles of % of monomer group be less than 10 moles %, less than 5 moles %, less than 1 mole %, less than 0.1 mole %, Less than 0.01 mole %, 0 mole of %；Relative to 100 mass % of monomer group be less than 10 mass %, less than 5 mass %, less than 1 Quality %, less than 0.5 mass %, less than 0.1 mass %, less than 0.01 mass %, 0 mass %.
<manufacturing method of water-soluble poly (methyl) acrylamide (A) of hydroxyl>
Water-soluble poly (methyl) acrylamide (A) of hydroxyl can be used various well known polymerizations and be synthesized, It is preferable to use radical polymerizations to be synthesized.Polymerization reaction can contain (a) ingredient and (b) ingredient and as needed (c) radical polymerization initiator and chain-transferring agent as needed are added in the monomer mixed solution of ingredient, is reacting while stirring - 100 DEG C of temperature 50 C or so lower progress.Reaction time is not particularly restricted, and preferably 1-10 hours or so.
Radical polymerization initiator can not be particularly restrictedly using various well known radical polymerization initiators.From It is, for example, by base polymerization initiator: the persulfates such as potassium peroxydisulfate and ammonium persulfate；Above-mentioned persulfate and sodium hydrogensulfite etc. The redox system polymerization initiator that reducing agent is combined；The azos systems such as 2,2 '-azo two (2- amidine propane) dihydrochlorides Initiator etc..The usage amount of radical polymerization initiator is not particularly restricted, the monomer group 100 relative to offer (A) ingredient Quality %, preferably 0.05 mass %-5.00 mass %, more preferably 0.1 mass %-3.0 mass %.
Before Raolical polymerizable and/or when obtained (A) ingredient is carried out water-solubleization etc., manufactured for improving The purpose of stability, also can be used the common neutralizer such as ammonia and organic amine, potassium hydroxide, sodium hydroxide, lithium hydroxide into The pH of row reaction solution is adjusted.In the case, pH is preferably 2-11.Meanwhile for the same purpose, conduct also can be used EDTA or its salt of metal ion sealant (metal イ オ Application sealing drug) etc..
In the case where water-soluble poly (methyl) acrylamide (A) of hydroxyl has acid groups, can adjust depending on the application Section be neutralization ratio appropriate (neutralization ratio 100% indicate using with it is contained in water-soluble poly (methyl) acrylamide (A) of hydroxyl The alkali of the identical molal quantity of sour component is neutralized；Neutralization ratio 50% indicates to utilize the water-soluble poly (methyl) third relative to hydroxyl The alkali of contained sour component half molal quantity is neutralized in acrylamide (A)) come carry out using.When dispersing electrode active material Neutralization ratio is not particularly restricted, after the formation such as coating, preferably 70%-120%, more preferably 80%-120%.Pass through Neutralization ratio after manufacturing above-mentioned coating becomes above range, and sour major part becomes the state being neutralized, will not be in battery With Li ion etc. in conjunction with and capacity reduction occurs, so being preferred.Neutralizing salt is, for example: Li salt, Na salt, K salt, ammonium salt, Mg Salt, Ca salt, Zn salt, Al salt etc..
<physical property of water-soluble poly (methyl) acrylamide (A) of hydroxyl>
In this application, " water solubility " refers to when being dissolved in the 0.5g compound in 100g water at 25 DEG C, insoluble matter Less than 0.5 mass %.
The glass transition point of water-soluble poly (methyl) acrylamide (A) of hydroxyl is not particularly restricted, and preferably 0 DEG C or more (10 DEG C or more, 20 DEG C with first-class)；From the viewpoint of mechanical strength, heat resistance, more preferably 30 DEG C or more (40 DEG C Above, 45 DEG C with first-class).
The glass transition temperature of water-soluble poly (methyl) acrylamide (A) of hydroxyl can be by containing (methyl) propylene The combination of the compound (a) of amide groups, (methyl) acrylate (b) of hydroxyl, comonomer (c) adjusts.In hydroxyl Water-soluble poly (methyl) acrylamide (A) in, glass transition temperature can by contain (methyl) acrylamido compound (a), glass transition temperature (Tg) (the absolutely temperature of (methyl) acrylate (b) of hydroxyl, the homopolymer of comonomer (c) Degree: K) and their mass fraction found out according to Fox formula as shown below.
1/Tg=(W1/Tg1)+(W2/Tg2)+(W3/Tg3)+…+(Wn/Tgn)
In formula, Tg indicates the glass transition temperature (K) for the polymer to be found out, W1-WnIndicate the quality point of each monomer Number, Tg1-TgnIndicate the glass transition temperature (K) of the homopolymer of each monomer.
For example, the homopolymer for acrylamide is 165 DEG C, for the equal of acrylic acid for glass transition temperature Polymers is 106 DEG C, and the homopolymer for hydroxy-ethyl acrylate is -15 DEG C, and the homopolymer for acrylonitrile is 105 DEG C.It is terrible To the trunk polymer (dry Port リ マ ー) (A) with desired glass transition temperature, in that case it can be decided that constitute the backbone polymerization The compound (a) containing (methyl) acrylamido of object (A), (methyl) acrylate (b) of hydroxyl, comonomer (c) Composition.In addition, the glass transition temperature of the homopolymer of monomer can pass through DSC (differential scanning calorimeter), DTA (differential heat Analytical equipment), TMA (thermomechanical measuring device) etc. be for example warming up to from -100 DEG C 300 DEG C condition (10 DEG C of heating rate/ Min it is measured under).In addition it is also possible to use the value recorded in document.Document is, for example, " Chemical manual basis piece II (chemistry Compile II in Bian list basis), (revision 5 editions) is compiled by Japanization association ", p325 etc..
Water-soluble poly (methyl) acrylamide (A) of hydroxyl solidfied material gelling divides rate not particularly restricted, (A) at The upper limit for the gelling point rate divided is, for example: 99.9%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25% Deng；Lower limit is, for example: 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 25%, 20% etc..Implement at one In mode, from the viewpoint of showing resistance to elastic effect along with charge and discharge cycles, preferably 20% or more, more preferably 25% or more.In addition, the gelling point rate of water-soluble poly (methyl) acrylamide (A) of hydroxyl refers to the value calculated by following formula:
Gelling divides rate (%)={ insoluble matter residue (g)/hard resin quality (g) in water } × 100 to implement at one In mode, the condition of cure of above-mentioned solidfied material is, for example, 4 hours etc. at 120 DEG C.
Above-mentioned gelling point rate is for example carried out as follows measurement.By water-soluble poly (methyl) propylene containing hydroxyl The lithium ion battery of amide (A) is added with amount appropriate (such as 10g) to container appropriate with heat cross-linking binder aqueous solution With appropriate in (such as ointment jar (manufactured by the production of Sogo Corporation's Physicochemical nitre, trade name " tinplate ointment jar ")) Drying condition (such as with circulated air drying machine (ADVANTECH Toyo Co., Ltd. manufactures, trade name " air-supply freeze-day with constant temperature machine DSR420DA ") 4 hours at 120 DEG C) it is dry after, the hard resin after obtaining heat cross-linking.By the quality of the hard resin 25 Correctly with quality meter appropriate, (such as Sartorius Amada Co., Ltd. is manufactured, trade name " standard balance at DEG C CPA324S ") measurement.By the hard resin of measurement be transferred to equipped with appropriate (such as 150mL) pure water appropriate containers (such as 300mL beaker) in, in water in the proper condition (such as 3 hours at 25 DEG C) using magnetic stirring apparatus appropriate (such as east Capital physics and chemistry instrument Co., Ltd. manufacture, trade name " strength magnetic stirring apparatus RCX-1000D ") under stirring conditions impregnate after, With utensil appropriate (such as using paulownia mountain funnel (Co., Ltd paulownia mountain production manufactured by, trade name " paulownia mountain funnel SB-60 ") and Attract clock (manufactured by the production of Co., Ltd paulownia mountain, trade name " attracting clock VKB-200 "), (Co., Ltd paulownia mountain makes institute to filter paper Manufacture, " No.50B ")) it is filtered under diminished pressure.Then, filter paper will be remained in drying machine appropriate (such as above-mentioned circulated air drying machine) On insoluble matter residue it is dry under condition appropriate (such as 3 hours at 120 DEG C) after, at temperature appropriate (such as 25 DEG C) Under correctly with the quality of quality meter appropriate (such as above-mentioned quality meter) measurement insoluble matter residue, calculated by above-mentioned formula water-soluble The gelling of resin after the heat cross-linking of adhesive for cell divides rate.
Mechanism
Containing from the chemical combination containing (methyl) acrylamido in water-soluble poly (methyl) acrylamide (A) of hydroxyl The hydroxyl of the amide groups of object (a) and (methyl) acrylate (b) from hydroxyl.They are due to passing through thermosetting chemical bond And carry out heat cross-linking.As a result, showing gelling point rate by insoluble in water.It is molten in lithium ion battery adhesive In liquid or aftermentioned lithium ion battery electrode slurry, amide groups and hydroxyl are individually present, therefore can show aqueous solution Storage stability or Stability of Slurry.In addition, a kind of this mechanism only theory, the present invention is not limited thereto.
The heat cross-linking for thinking water-soluble poly (methyl) acrylamide (A) of hydroxyl is that origin is derived from containing (methyl) acryloyl The amide groups of the compound (a) of amido and caused by the hydroxyl of (methyl) acrylate (b) of hydroxyl.In hydroxyl Water-soluble poly (methyl) acrylamide (A) in, the molar ratio (amide groups/hydroxyl) of amide groups and hydroxyl is not limited especially Fixed, preferred amide base is superfluous.The upper limit of the molar ratio (amide groups/hydroxyl) of amide groups and hydroxyl is, for example: 19,18,17.5, 15,12.5,10,9,7.5,5,2.5,1.2 etc.；Lower limit is, for example: 18,17.5,15,12.5,10,9,7.5,5,2.5,1.2, 1.0 waiting.In one embodiment, it is preferred to amide groups/hydroxyl=1.0-19.0, more preferable 1.2-18.0.Meet above-mentioned condition When, it is believed that it can obtain showing with charge and discharge cycles in the case where not damaging adhesiveness of the active material layer to collector Resistance to elastic effect, but do not mean that and limit the invention to this.
The weight average molecular weight (Mw) of water-soluble poly (methyl) acrylamide (A) of hydroxyl is not particularly restricted, thereon Limit is, for example: 6,000,000,5,500,000,5,000,000,4,500,000,4,000,000,3,500,000,3,000,000,2,500,000,2,000,000,1,500,000,1,000,000,95 Ten thousand, 900,000,850,000,800,000,750,000,700,000,650,000,600,000,550,000,500,000,450,000,400,000 etc.；Lower limit is, for example: 5,500,000, 5000000,4,500,000,4,000,000,3,500,000,3,000,000,2,900,000,2,500,000,2,000,000,1,500,000,1,000,000,950,000,900,000,850,000,80 Ten thousand, 750,000,700,000,650,000,600,000,550,000,500,000,450,000,400,000,350,000,300,000 etc..In one embodiment, from lithium From the viewpoint of the dispersion stabilization of ion battery electrode slurry, preferably 300,000-600 ten thousand, more preferably 350,000-600 ten thousand.
The number-average molecular weight (Mn) of water-soluble poly (methyl) acrylamide (A) of hydroxyl is not particularly restricted, thereon Limit is, for example: 6,000,000,5,500,000,5,000,000,4,500,000,4,000,000,3,500,000,3,000,000,2,500,000,2,000,000,1,500,000,1,000,000,95 Ten thousand, 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 Deng；Lower limit is, for example: 5,500,000,5,000,000,4,500,000,4,000,000,3,500,000,3,000,000,2,900,000,2,500,000,2,000,000,1,500,000,100 Ten thousand, 950,000,900,000,850,000,800,000,750,000,700,000,650,000,600,000,550,000,500,000,450,000,400,000,350,000,300,000,20 Ten thousand, 100,000,50,000,10,000 etc..In one embodiment, the number of water-soluble poly (methyl) acrylamide (A) of hydroxyl is divided equally Son amount (Mn) is preferably 10,000 or more.
Weight average molecular weight and number-average molecular weight for example measure under appropriate solvent as by gel permeation chromatography (GPC) Polyacrylic acid scaled value find out.
The upper limit of the molecular weight distribution (Mw/Mn) of water-soluble poly (methyl) acrylamide (A) of hydroxyl is, for example: 15, 14,13,11,10,9,7.5,5,4,3,2.9,2.5,2,1.5 etc.；Lower limit is, for example: 14,13,11,10,9,7.5,5,4,3, 2.9,2.5,2,1.5,1.1 etc..In one embodiment, the molecule of water-soluble poly (methyl) acrylamide (A) of hydroxyl Amount distribution (Mw/Mn) is preferably 1.1-15.
The Type B viscosity of the aqueous solution of water-soluble poly (methyl) acrylamide (A) containing hydroxyl is not particularly restricted, Its upper limit is, for example: 100,000 mPas, 90,000 mPas, 80,000 mPas, 70,000 mPas, 60,000 mPas, 50,000 mPas, 40,000 MPas, 30,000 mPas, 20,000 mPas, 10,000 mPas, 9000mPas, 8000mPas, 7000mPas, 6000mPas, 5000mPas, 4000mPas, 3000mPas, 2000mPas etc.；Lower limit be, for example, 90,000 mPas, 80000 mPas, 70,000 mPas, 60,000 mPas, 50,000 mPas, 40,000 mPas, 30,000 mPas, 20,000 mPas, 10,000 mPa·s、9000mPa·s、8000mPa·s、7000mPa·s、6000mPa·s、5000mPa·s、4000mPa·s、 3000mPas, 2000mPas, 1000mPas etc..In one embodiment, Type B viscosity ranges preferably from Ten thousand mPas of 1000mPas-10.In addition, Type B viscosity uses Toki Sangyo Co., Ltd.'s manufacture, trade name " Brookfield viscometer BM The Brookfield viscometer of type " etc. is measured.
The upper limit of the pH (25 DEG C) of the aqueous solution of water-soluble poly (methyl) acrylamide (A) containing hydroxyl is, for example: 13,12,11,10,9,8,7,6.9,6.5,6,5.9,5.6,5.5,5.4,5,4.5,4,3,2.5 etc.；11 lower limit is, for example: 12, 10,9,8,7,6.9,6.5,6,5.9,5.6,5.5,5.4,5,4.5,4,3,2.5,2 etc..In one embodiment, from solution From the viewpoint of stability, the pH (25 DEG C) of the aqueous solution of water-soluble poly (methyl) acrylamide (A) containing hydroxyl is preferred For pH 2-13, more preferably pH 2-9, further preferably pH 2-7, particularly preferred pH is less than 7.The pH of aqueous solution can make It is measured at 25 DEG C with glass electrode pH meter (such as Horiba Ltd manufactures, trade name " pH meter D-52 ").
Relative to lithium ion battery 100 mass % of binder aqueous solution, water-soluble poly (methyl) acryloyl of hydroxyl The upper limit of the content of amine (A) is, for example: 20 mass %, 19 mass %, 15 mass %, 14 mass %, 12 mass %, 10 matter Measure %, 9 mass %, 7 mass %, 6 mass % etc.；Lower limit is, for example: 19 mass %, 15 mass %, 14 mass %, 12 matter Measure %, 10 mass %, 9 mass %, 7 mass %, 6 mass %, 5 mass % etc..In one embodiment, relative to lithium ion The content of 100 mass % of adhesive for cell aqueous solution, water-soluble poly (methyl) acrylamide (A) of hydroxyl are preferably 5 matter Measure %-20 mass %.
<additive>
Lithium ion battery is not equivalent to the examination of any one of (A) ingredient and water with that can contain in binder aqueous solution Agent is as additive.Additive is, for example: dispersing agent, levelling agent, antioxidant, tackifier, dispersion (lotion), crosslinking agent, Silicol base (ヒ De ロ キ シ シ リ Le) compound etc..Relative to 100 mass % of (A) ingredient, the content of additive is for example Be: 0-5 mass %, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass % etc.；In addition, relative to aqueous solution 100 The content of quality %, additive are, for example: 0-5 mass %, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, 0 mass % etc..
Dispersing agent can be selected according to the electrode active material used, e.g.: anionic property dispersing agent, cationic point Powder, nonionic dispersing agent, macromolecule dispersing agent etc..
Levelling agent is, for example: alkyl system surfactant, silicon-based surfactant, fluorine system surfactant, metal system table Surfactants such as face activating agent etc..By using surfactant, the shrinkage cavity (は じ I) generated when coating, Ke Yiti are prevented The flatness of the layer (coating) of high above-mentioned slurry.
Antioxidant is, for example: phenolic compounds, hydroquinone compound, organic phosphine compound, sulphur compound, phenylenediamine Close object, polymer-type phenolic compounds etc..Polymer-type phenolic compounds is polymer in the molecule with phenol structure.Polymer-type The weight average molecular weight of phenolic compounds is preferably 200-1000, more preferably 600-700.
Tackifier are, for example: the cellulose-based polymer such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose and Their ammonium salt and alkali metal salt；(modification) poly- (methyl) acrylic acid and their ammonium salt and alkali metal salt；(modification) poly- second The copolymer of enol, acrylic acid or acrylates and vinyl alcohol, maleic anhydride or maleic acid or fumaric acid and vinyl alcohol are total to The polyvinyl alcohols such as polymers；Polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, modified polyacrylic acid, oxidized starch, Starch phosphate, casein, various modified starches, acrylonitrile-butadiene copolymer hydride etc..
Dispersion (lotion) is, for example: styrene-butadiene system copolymer emulsion, gathers polystyrenic polymer latex Butadiene-based polymer emulsion, acrylonitrile-butadiene based copolymer latex, polyurethane series polymer latex, polymethylacrylic acid Methyl esters based polymer latex, methyl methacrylate-butadiene-based copolymer emulsion, polyacrylate based polymer latex, chlorine Ethylene-based polymer latex, vinyl acetate system polymer emulsion, vinyl based copolymer lotion, polyethylene cream Liquid, carboxy-modified styrenebutadiene copolymer resin emulsion, emulsion acrylic resin, polyethylene, polypropylene, poly terephthalic acid Glycol ester, polyamide (PA), polyimides (PI), polyamidoimide (PAI), aromatic polyamides, alginic acid and its salt gather Vinylidene (PVDF), polytetrafluoroethylene (PTFE) (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkane Base vinyl ether co-polymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) etc..
Crosslinking agent is, for example: formaldehyde, glyoxal, hexa, urea-formaldehyde resin, melamine methylol tree Rouge, carbodiimide compound, multi-group epoxy compound, oxazoline compound, polyfunctional group hydrazide compound, isocyanic acid Ester compounds, melamine compound, urea compounds and their mixture.
Silicol based compound refers to the compound for the structure for having hydroxyl (- OH) with Direct Bonding on the silicon atoms, Ortho-siliformic acid based compound refers to ortho-siliformic acid base (- Si (OH)3) compound, tetrahydroxy silane-based compound is Refer to by Si (OH)4The compound of expression.In one embodiment, ortho-siliformic acid based compound is indicated by the following general formula Compound:
RSi(OH)3
In formula, R indicates substituted or unsubstituted alkyl, vinyl or (methyl) acryloxy；Above-mentioned substituent group is for example It is: amino, sulfydryl, glycidoxypropyl (グ リ シ De キ シ yl), (methyl) acryloxy, epoxy group etc..Silicol base Compound is preferably by preparing silane coupling agent or tetraalkoxysilane hydrolysis.Silicol based compound can also be not It loses and carries out part polycondensation in water-soluble range.Usually used silane coupling agent can be used in silane coupling agent.Silane is even It is not particularly restricted to join agent.It can be used alone by the silicol based compound that silane coupling agent manufactures, also can be used together 2 Kind or more.In one embodiment, silicol based compound includes ortho-siliformic acid base propylamine.Trialkoxy silane is for example It is: 3- TSL 8330,3-aminopropyltriethoxysilane, N-2 (amino-ethyl) 3- aminopropyl front three Oxysilane, N-2 (amino-ethyl) 3-aminopropyltriethoxysilane, 3- triethoxysilicane alkyl-N- (1,3- dimethyl- Butylidene) propylamine, N- phenyl -3- TSL 8330,3-mercaptopropyi trimethoxy silane, 3- isocyanates third Ethyl triethoxy silicane alkane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- methacryloxypropyl front three Oxysilane, 3- methacryloxypropyl, 3- acryloyloxypropyltrimethoxysilane, tetrahydroxy Silane etc..In addition, tetraalkoxysilane is, for example: tetramethoxy-silicane, tetramethoxy-silicane oligomer, tetraethoxysilane, Tetraethoxysilane oligomer etc..Wherein, it is preferable to use 3- aminopropyl three from the viewpoint of stability and electrolyte resistance Methoxy silane manufactures silicol based compound.
As additive other than the above, e.g. selected from by unsaturated carboxylic acid, unsaturated amides and their salt At least one kind of compound in the group of composition etc..
Above-mentioned lithium ion battery can be used as negative electrode of lithium ion battery heat cross-linking with heat cross-linking binder aqueous solution Binder aqueous solution come using, can also be used as lithium ion cell positive with heat cross-linking binder aqueous solution come using.
[2. lithium ion battery electrode slurry]
This application provides lithium ion battery electrode slurry, the lithium ion battery electrode slurry contain above-mentioned lithium from Sub- battery heat cross-linking binder aqueous solution and electrode active material (B).
<electrode active material (B) (also referred to as (B) ingredient)>
As long as the substance of lithium can reversibly be received and be discharged, electrode active material is not particularly restricted, Ke Yidan It solely uses, also can be used together two or more.Electrode active material can suitably be selected according to the type of electrical storage device as a purpose Select suitable material.Electrode active material is, for example: carbon material and silicon materials, the oxide containing lithium atom, lead compound, Tin compound, arsenic compound, antimonial and aluminium compound etc. and the material of lithium alloyage etc..Carbon material and with lithium alloyage Material can play effect of the invention since the cubical expansivity when battery charges is big significantly.
Above-mentioned carbon material is, for example: graphite (also referred to as blacklead, such as natural graphite, artificial graphite as highly crystalline carbon Deng), low crystalline carbon (soft carbon, hard carbon), carbon black (black, thermal black of Ketjen black, acetylene black, channel black, lampblack, oil oven etc.), fowler Alkene, carbon nanotube, carbon nano-fiber, carbon nanohorn, carbon fiber silk, carbonaceous mesophase spherules (MCMB), pitch-based carbon fiber etc..
Above-mentioned silicon materials are other than silicon, silica, silicon alloy, such as also: SiC；SiOxCy(0 x≤3 <, 0 < y≤ 5)；Si3N4；Si2N2O；By SiOxThe silica composite that (0 x≤2 <) indicate is (such as in Japanese Unexamined Patent Publication 2004-185810 public affairs The material etc. recorded in report and Japanese Unexamined Patent Publication 2005-259697 bulletin)；Remember in Japanese Unexamined Patent Publication 2004-185810 bulletin The silicon materials etc. of load.It is also possible to use recorded in Japanese Patent Publication No. 5390336, Japanese Patent Publication No. 5903761 Silicon materials.
Above-mentioned silica is preferably by structural formula SiOxThe silica that (0 < x < 2, preferably 0.1≤x≤1) indicates.
Above-mentioned silicon alloy is preferably the alloy of silicon Yu at least one transition metal, the transition metal be selected from by titanium, zirconium, The group of nickel, copper, iron and molybdenum composition.The silicon alloy of these transition metal is with high electron conductivity and has high intensity, so excellent Choosing.Silicon alloy is more preferably silicon-nickel alloy or silicon-titanium alloy, particularly preferably silicon-titanium alloy.Relative in above-mentioned alloy 100 moles of % of metallic element, the content ratio of silicon is preferably 10 moles of % or more in silicon alloy, more preferably 20 moles of %- 70 moles of %.In addition, silicon materials can be any one of monocrystalline, polycrystalline and amorphous.
In addition, the electrode active other than silicon materials can be used together in the case where using silicon materials as electrode active material Property substance.Such electrode active material is, for example: above-mentioned carbon material；The electroconductive polymers such as polyacene；By AXBYOZ(A is indicated Alkali metal or transition metal；B indicates at least one selected from by transition metal such as cobalt, nickel, aluminium, tin, manganese；O indicates that oxygen is former Son；X, Y and Z is the number of the range of 0.05 < X < 1.10,0.85 < Y < 4.00,1.5 < Z < 5.00 respectively) indicate compound Metal oxide；And other metal oxides etc..In the case where using silicon materials as electrode active material, with lithium The volume change for receiving and discharging and occurring is small, and it is advantageous to be used in combination with carbon material.
The above-mentioned oxide containing lithium atom is, for example: ternary system nickle cobalt lithium manganate, lithium-manganese composite oxide (LiMn2O4 Deng), lithium-ni compound oxide (LiNiO2Deng), lithium-cobalt composite oxide (LiCoO2Deng), lithium-iron composite oxides (LiFeO2 Deng), lithium-nickel-manganese composite oxide (LiNi0.5Mn0.5O2Deng), lithium-nickel-cobalt composite oxides (LiNi0.8Co0.2O2Deng), lithium- Transition metal phosphate compound (LiFePO4Deng) and lithium-transition metal sulphate (LixFe2(SO4)3), lithium-titanium composite oxygen Compound (lithium titanate: Li4Ti5O12) etc. lithiums-compound transition metal oxide and other previously known electrode active material etc..
The shape of electrode active material is not particularly restricted, can be the arbitrary shape such as microgranular, film-form, preferably It is microgranular.The average grain diameter of electrode active material is not particularly restricted, and the upper limit is, for example: 50 μm, 45 μm, 40 μm, 35 μ M, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 4 μm, 3 μm, 2.9 μm, 2 μm, 1 μm, 0.5 μm, 0.1 μm etc.；Lower limit is, for example, 45μm、40μm、35μm、30μm、25μm、20μm、15μm、10μm、5μm、4μm、3μm、2.9μm、2μm、1μm、0.5μm、0.1μm Deng.In one embodiment, it is preferred to be 0.1 μm -50 μm.If if 0.1 μm or more operability it is good, if 50 μm with Under then be easy carry out electrode coating.More preferably 0.1 μm -45 μm, further preferably 1 μm -10 μm, particularly preferably 5 μm Left and right.If in such range uniform and thin film can be formed, therefore preferably.In addition, " the grain in the application Diameter " refers to the maximum distance in the distance between any two points on the contour line of particle.In addition, if not referring in particular to Out, the value of " average grain diameter ", which refers to, observes hand using scanning electron microscope (SEM) and transmission electron microscope (TEM) etc. Section, using the calculated value of mean particle size institute in several particles observed into the dozens of visual field.
In order to play effect of the invention significantly, the carbon material and/or and lithium alloy contained in electrode active material The material of change is preferably 50 mass % or more, more preferably 80 mass % or more, further preferably 90 mass % or more, especially It is preferred that 100 mass %.
In one embodiment, from the viewpoint of the battery capacity for improving lithium ion battery, relative to electrode activity The content of 100 mass % of substance, the silicon or silica that are covered in electrode active material by carbon-coating are preferably 5 mass % or more (example As 10 mass % or more, 20 mass % or more, 30 mass % or more, 40 mass % or more, 50 mass % or more, 60 mass % with Upper, 70 mass % or more, 80 mass % or more, 90 mass % or more, 100 mass %).
Relative to 100 mass % of slurry of the invention, the upper limit of the content of (A) ingredient is, for example: 15 mass %, 14 matter Measure %, 12 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 matter Measure %, 0.9 mass %, 0.6 mass % etc.；Lower limit is, for example, 14 mass %, 12 mass %, 10 mass %, 9 mass %, 7 matter Measure %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.9 mass %, 0.6 mass %, 0.5 mass % etc.. In one embodiment, relative to 100 mass % of slurry of the invention, the content of (A) ingredient is preferably 0.5 mass %-10 Quality %.
In slurry of the invention, the content of above-mentioned (A) ingredient is not particularly restricted, relative to 100 matter of (B) ingredient % is measured, the upper limit of (A) component content is, for example: 15 mass %, 14 mass %, 11 mass %, 10 mass %, 9 mass %, 5 matter Measure %, 4 mass %, 2 mass % or so；Lower limit is, for example, 14 mass %, 11 mass %, 10 mass %, 9 mass %, 5 matter Measure %, 4 mass %, 2 mass %, 1 mass % or so.In one embodiment, relative to 100 mass % of (B) ingredient, (A) Ingredient is preferably 1 mass %-15 mass % or so.
In addition, the content of above-mentioned (B) ingredient is not particularly restricted, relative to of the invention in slurry of the invention 100 mass % of slurry, the upper limit of the content of (B) ingredient is, for example: 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass % etc.；Lower limit is, for example, 60 mass %, 55 mass %, 50 Quality %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass % etc..In an embodiment In, relative to 100 mass % of slurry of the invention, the content of (B) ingredient is preferably 20 mass %-65 mass %.
In addition, water-soluble poly (the first of hydroxyl also can be used in lithium ion battery electrode slurry of the invention Base) adhesive other than acrylamide (A), but water-soluble poly (methyl) acrylamide (A) of the hydroxyl in whole adhesives Preferably 90 mass % or more (95 mass % or more, 99 mass % or more, 100 mass % etc.).
(slurry viscosity adjustment solvent)
Slurry viscosity is adjusted solvent and can not be can be used alone particularly restrictedly using various well known solvents, Also it can be used together two or more.Above-mentioned solvent is, for example: ether solvents, ketone solvent, alcoholic solvent, amide solvent, water etc..Ether solvents example It is in this way: dioxane, tetrahydrofuran (THF) etc..Ketone solvent is, for example: acetone, methyl ethyl ketone (MEK) etc..Alcoholic solvent is for example It is: methanol, ethyl alcohol, 2- propyl alcohol, isopropanol etc..Amide solvent is, for example: n-methyl-2-pyrrolidone (NMP) etc..
It is had attempted to so far by adding crosslinking agent in adhesive or slurry, on the current collector simultaneously by slurry coating It makes it dry to make adhesive resin heat cross-linking (such as the material recorded in International Publication No. 2015/098507 in electrode Deng).As a result, by being crosslinked the adhesive resin in electrode, has and inhibit to expand with the active material layer of charge and discharge cycles Effect.In heat cross-linking binder solution of the invention, by making the adhesive resin heat cross-linking in electrode, it may have suppression Make the effect expanded with the active material layer of charge and discharge cycles.Heat cross-linking binder solution of the invention has used the heat The excellent storage stability of the heat cross-linking electrode slurry of bridging property binder solution.The evaluation method of storage-stable can lead to Cross evaluation of such as getting off: with the heat cross-linking binder solution of Brookfield viscometer measurement production or the solution of heat cross-linking electrode slurry It after viscosity, is stored 3 days in the baking oven for being warming up to 40 DEG C, then measures the solution viscosity after storage with Brookfield viscometer, confirm viscosity The presence or absence of variation.
<additive>
It can contain in above-mentioned slurry and not be equivalent to the reagent of any one of (A) ingredient, (B) ingredient and water as adding Add agent.Relative to above-mentioned 100 mass % of slurry, the content of additive is, for example: 0-5 mass %, less than 1 mass %, less than 0.1 Quality %, less than 0.01 mass %, 0 mass % etc..In addition, additive is, for example, above-mentioned additive etc..
Above-mentioned lithium ion battery can be used as negative electrode of lithium ion battery with electrode slurry come using can also be with electrode slurry As lithium ion cell positive with electrode slurry come using.
[manufacturing methods of 3. lithium ion battery electrode slurrys]
This application provides the manufacturing method of above-mentioned lithium ion battery electrode slurry, the method includes by hydroxyl The step of water-soluble poly (methyl) acrylamide (A) and electrode active material (B) mix, wherein the hydroxyl it is water-soluble Property poly- (methyl) acrylamide (A) solidfied material gelling point rate be 20% or more and be the polymer of following monomer groups: it is opposite In 100 moles of % of monomer group, the monomer group contains the compound containing (methyl) acrylamido of 30 moles of %-95 moles of % (a), (methyl) acrylate (b) of the hydroxyl of 5 moles of %-50 moles of %.
The manufacturing method of slurry of the invention is, for example: by aqueous solution (the above-mentioned lithium ion battery adhesive of (A) ingredient Aqueous solution) and electrode active material mixing method；The method that (A) ingredient, (B) ingredient, water are mixed respectively.In addition, upper It states in method, order by merging is not particularly restricted.The mixed media of slurry is, for example: ball mill, sand mill, pigment dispersion Machine, mixing and kneading machine, ultrasonic dispersing machine, homogenizer, planetary stirring machine, Hobart's blender etc..
[4. lithium ion battery electrode]
This application provides lithium ion battery electrode, the lithium ion battery electrode is by by lithium ion battery electricity consumption Pole slurry is coated on the current collector and makes it dry and obtains.
Coating means are not particularly restricted, e.g.: comma coating machine, gravure coater, micro gravure coating machine, mould Have the previously known coating units such as coating machine, metering bar coater.
Drying means is not also particularly restricted, and temperature is preferably 80 DEG C -200 DEG C or so, and more preferably 90 DEG C -180 DEG C Left and right；Atmosphere is dry air or inert atmosphere.By being dried at a proper temperature, carry out as lithium ion The crosslinking of water-soluble poly (methyl) acrylamide (A) of the battery hydroxyl of heat cross-linking adhesive is shown with charge and discharge The resistance to resilience of electricity circulation.
The thickness of electrode (cured coating film) is not particularly restricted, and preferably 5 μm -300 μm or so, more preferably 10 μm - 250 μm or so.By being set as above range, sufficient Li can be readily derived for highdensity current value and inhaled The function of receiving-discharge.
Collector can not be particularly restrictedly using various well known collectors.The material of collector is not by special It limits, e.g.: the metal materials such as copper, iron, aluminium, nickel, stainless steel, nickel-plated steel；And the carbon materials such as carbon cloth, carbon paper.Collector Form it is also not particularly restricted, in the case where metal material, e.g. metal foil, metal cylinder, wire coil, metal Plate etc.；In the case where carbon material, e.g. carbon plate, C film, carbon cylinder etc..Wherein, electrode active material is being used to bear In the case where pole, use copper foil as collector in present industrial product, it is advantageous to.
Above-mentioned lithium ion battery can be used as negative electrode of lithium ion battery with electrode come using can also be used as lithium ion battery Anode uses.
[5. lithium ion battery]
This application provides the lithium ion batteries comprising above-mentioned lithium ion battery electrode.Also comprising electrolysis in above-mentioned battery Matter solution, diaphragm, anode and packaging material, these are not particularly restricted.
Electrolyte solution is, for example, the non-aqueous electrolyte etc. that supporting electrolyte has been dissolved in non-aqueous solvent.In addition, Overlay film forming agent can also be contained in above-mentioned non-aqueous electrolyte.
Non-aqueous solvent can not be can be used alone with being particularly restricted using various well known non-aqueous solvents, Also it can be used together two or more.Non-aqueous solvent is, for example: the chains carbon such as diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate Acid esters solvent；The cyclic carbonate solvents such as ethylene carbonate, propylene carbonate, butylene carbonate；1,2- dimethoxy-ethane etc. Chain ether solvents；The ring-type ether solvents such as tetrahydrofuran, 2- methyltetrahydrofuran, sulfolane, 1,3- dioxolanes；Methyl formate, The chains ester solvent such as methyl acetate, methyl propionate；The ring-type ester solvent such as gamma-butyrolacton, gamma-valerolactone；Acetonitrile etc..Wherein, excellent Select the combination of the mixed solvent containing cyclic carbonate and linear carbonate.
Lithium salts can be used in supporting electrolyte.Lithium salts can not be with being particularly restricted using various well known lithium salts, can To be used alone, also can be used together two or more.Supporting electrolyte is, for example: LiPF6、LiAsF6、LiBF4、LiSbF6、 LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLi Deng.Wherein, it is preferably easy dissolution in a solvent and shows the LiPF of high dissociation degree6、LiClO4、CF3SO3Li.It is got over using degree of dissociation High supporting electrolyte, lithium ion conduction degree is higher, therefore, can adjust lithium ion conduction by the type of supporting electrolyte Degree.
Overlay film forming agent can not be can be used alone with being particularly restricted using various well known overlay film forming agents, Also it can be used together two or more.Overlay film forming agent is, for example: vinylene carbonate base ester, ethylene carbonate base ethylidene ester, carbonic acid second The carbonate products such as alkenyl ethyl ester, methyl phenylester, carbonic acid fluoroethylene ester, two fluoroethylene ester of carbonic acid；Ring The epithios alkane such as sulphur ethane, epithio propane；The sultone compounds such as 1,3- propane sultone, 1,4- butane sultone；Maleic acid Acid anhydrides such as acid anhydride, succinic anhydride etc..The content of overlay film forming agent is not particularly restricted in electrolyte solution, according to 10 mass % with Under, 8 mass % or less, 5 mass % or less and 2 mass % sequences below it is preferred.By making content in 10 mass % hereinafter, covering The advantages of film forming agent, is: can be readily derived mentioning for the inhibition of initial stage irreversible capacity, low-temperature characteristics and multiplying power property It is high.
Diaphragm be between anode and cathode between article, in order to prevent it is interelectrode short circuit and use.Specifically, can To impregnate these diaphragms with above-mentioned non-aqueous electrolyte and use it is preferable to use the porous diaphragm such as perforated membrane and non-woven fabrics. The polyolefin such as polyethylene, polypropylene, polyether sulfone etc., preferred polyolefm can be used in the material of diaphragm.
In addition, using electrode slurry using above-mentioned lithium ion battery and the cathode that manufactures as cathode and uses not using Electrode slurry is used using above-mentioned lithium ion battery and in the case that the anode that manufactures manufactures lithium ion battery as anode, anode It can not be particularly restrictedly using various well known anodes.Anode be, for example, by by positive active material, conductive auxiliary agent, Positive electrode binder mixes to prepare slurry with organic solvent, and the slurry by that will prepare is coated on positive electrode collector, is dry Anode obtained from dry, compacting etc..
Positive active material is, for example: inorganic positive active material, organic positive active material.Inorganic positive active material E.g.: transition metal oxide, the composite oxides of lithium and transition metal, transient metal sulfide etc..Above-mentioned transition metal E.g.: Fe, Co, Ni, Mn, Al etc..Inorganic compound used in positive active material is, for example: LiCoO2、LiNiO2、 LiMnO2、LiMn2O4、LiFePO4、LiNi1/2Mn3/2O4、LiCo1/3Ni1/3Mn1/3O2、Li[Li0.1Al0.1Mn1.8]O4、LiFeVO4 Deng the metal composite oxide containing lithium；TiS2、TiS3, amorphous MoS2Equal transient metal sulfides；Cu2V2O3, amorphous V2O-P2O5、 MoO3、V2O5、V6O13Equal transition metal oxides etc..These compounds are also possible to the compound of Partial Elements substitution.It is organic just Pole active material is, for example, the electric conductive polymers such as polyacetylene, polyparaphenylene.By there is carbon source material in reductive firing, The ferrous oxide of poorly conductive can also be used as carbon material covering electrode active material come using.In addition, these compounds It is also possible to the compound of Partial Elements substitution.Wherein, from practicability, electrical characteristics, from the viewpoint of the long-life, preferably LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiFePO4、LiNi1/2Mn3/2O4、LiCo1/3Ni1/3Mn1/3O2、Li [Li0.1Al0.1Mn1.8]O4。
Conductive auxiliary agent is, for example, the fibres such as gas-phase growth of carbon fibre (VGCF), carbon nanotube (CNT), carbon nano-fiber (CNF) Tie up shape carbon；The carbon blacks such as graphite particle, acetylene black, Ketjen black, oil oven be black；Average grain diameter 10 μm of Cu, Ni, Al, Si below or it The micro mist etc. that is formed of alloy.
Positive electrode binder can not be can be used alone particularly restrictedly using various well known adhesives, It can be used together two or more.Positive electrode binder is, for example: fluorine resin (Kynoar, polytetrafluoroethylene (PTFE) etc.), polyolefin (polyethylene, polypropylene etc.), polymer (SBR styrene butadiene rubbers, isoprene rubber, butadiene with unsaturated bond Rubber etc.), acrylic acid series polymeric compounds (acrylic copolymer, methacrylic acid copolymer etc.) etc..
Positive electrode collector is, for example, aluminium foil, stainless steel foil etc..
The form of above-mentioned lithium ion battery is not particularly restricted.The form of lithium ion battery is, for example: making electrode slice (シ ー ト electrode) and diaphragm become spiral helicine column type；By plate electrode (ペ レ ッ ト electrode) and diaphragm be combined it is interior towards The column type of (イ Application サ イ De ア ウ ト) structure outside；Plate electrode and diaphragm are carried out to button-shaped (the U イ Application タ イ of lamination プ) etc..Meanwhile by can be made coin shape, cylinder type, side in the battery outer of these forms unexpected packing box in office The arbitrary shape such as type uses.
The manufacturing method of above-mentioned lithium ion battery is not particularly restricted, takes program groups appropriate according to the structure of battery Dress.The manufacturing method of lithium ion battery is, for example, method documented by Japanese Unexamined Patent Publication 2013-089437 bulletin etc..It can be with Cathode is loaded on external packing box, and electrolyte and diaphragm are set on cathode, is loaded on anode, keeps positive electrode and negative electrode opposite, by Gasket (ガ ス ケ ッ ト), hush panel are fixed to manufacture battery.
Embodiment
Hereinafter, being illustrated in more details by embodiment and comparative example to the present invention, but the present invention is not limited thereto.Separately Outside, without illustrating, " % " expression " quality % ", " part " expression " mass parts " in embodiment.
The manufacture of (1. A) ingredient
Embodiment 1-1
With blender, thermometer, reflux condensing tube, nitrogen ingress pipe reaction unit in ion exchange water is added 1020g, 50% acrylamide aqueous solution 250g (1.76mol), acrylamide tert-butyl sulfonic acid 22.4g (0.108mol), propylene Sour 2- hydroxyl ethyl ester 33.9g (0.292mol), Sodium methallyl sulfonate (メ タ リ Le ス Le ホ Application acid Na ト リ ウ system) 0.34g (0.0022mol) is warming up to 50 DEG C after removing the oxygen in reaction system by nitrogen.2,2 '-azo, two (2- is put into thereto Amidine propane) dihydrochloride (Nippoh Chemicals Co., Ltd's manufacture, trade name " NC-32 ") 1.8g, ion exchange water 50g, heating Reaction 3 hours is carried out to 80 DEG C, obtains the aqueous solution of the water-soluble polyacrylamide containing hydroxyl.
Embodiment 1-2~embodiment 1-9
In addition to will form and measure shown in the quantitative change of monomer composition and initiator in above-described embodiment 1-1 more table 1 In addition, other to be operated in a manner of same as embodiment 1-1, prepare the water of the water-soluble polyacrylamide containing hydroxyl Solution.
Comparative example 1-1
With blender, thermometer, reflux condensing tube, nitrogen ingress pipe reaction unit in ion exchange water is added 1000g, 50% acrylamide aqueous solution 380g (2.67mol), Sodium methallyl sulfonate 0.42g (0.0027mol), pass through nitrogen After gas removes the oxygen in reaction system, it is warming up to 50 DEG C.2,2 '-azo two (2- amidine propane) dihydrochlorides are put into thereto (Nippoh Chemicals Co., Ltd manufacture, trade name " NC-32 ") 1.9g, ion exchange water 50g, being warming up to 80 DEG C, to carry out reaction 3 small When, obtain the aqueous solution containing polyacrylamide.
Comparative example 1-2~comparative example 1-3
In addition to composition shown in the quantitative change more table 1 by the monomer composition and initiator in above-mentioned comparative example 1-1 and measure In addition, other to be operated in a manner of same as comparative example 1-1, preparation is water-soluble containing water-soluble poly (methyl) acrylamide Liquid.
Comparative example 1-4
With blender, thermometer, reflux condensing tube, nitrogen ingress pipe reaction unit in ion exchange water is added 990g, 50% acrylamide aqueous solution 190g (1.34mol), 80% acrylic acid 80.4g (0.892mol), methallyl sulfonic acid Sodium 0.35g (0.0022mol) is warming up to 50 DEG C after removing the oxygen in reaction system by nitrogen.It is even that 2,2 '-are put into thereto Nitrogen two (2- amidine propane) dihydrochloride (Nippoh Chemicals Co., Ltd's manufacture, trade name " NC-32 ") 1.6g, ion exchange water 50g is warming up to 80 DEG C and carries out reaction 3 hours.It then cools to room temperature, carbodiimide compound 14.8g (Nisshinbo ケ is added ミ カ Le Co., Ltd. " カ Le ボ ジ ラ イ ト V-02 "), obtain the aqueous solution containing polyacrylamide and crosslinking agent.
Type B viscosity
Using Brookfield viscometer, (Toki Sangyo Co., Ltd. manufactures the viscosity of each binder aqueous solution, trade name " Type B viscosity Meter BM type ") it is measured at 25 DEG C according to the following conditions.
In the case where viscosity 100,000mPas-20,000mPas: using No.4 rotor, revolution 6rpm；In viscosity In the case where less than 20,000mPas: using No.3 rotor, revolution 6rpm.
Weight average molecular weight
Weight average molecular weight be used as by gel permeation chromatography (GPC) 0.2M phosphate buffer/acetonitrile solution (90/10, PH8.0 the polyacrylic acid scaled value measured under) is found out.GPC device is manufactured using HLC-8220 (Dong ソ ー (Co., Ltd.)), column It uses SB-806M-HQ (SHODEX manufacture).
Gelling divides rate
By the lithium ion battery heat cross-linking adhesive water of water-soluble poly (methyl) acrylamide (A) containing hydroxyl Solution 10g is put into ointment jar (manufactured by the production of Sogo Corporation's Physicochemical nitre, trade name " tinplate ointment jar "), uses Circulated air drying machine (manufacture of ADVANTECH Toyo Co., Ltd., trade name " air-supply freeze-day with constant temperature machine DSR420DA ") is at 120 DEG C After drying in lower 4 hours, the hard resin after obtaining heat cross-linking.By the quality of the hard resin correctly with quality meter at 25 DEG C (manufacture of Sartorius Amada Co., Ltd., trade name " standard balance CPA324S ") measurement.The hard resin of measurement is turned It moves on in the container (300mL beaker) equipped with 150mL pure water, uses magnetic stirring apparatus (Tokyo physics and chemistry device at 25 DEG C in water The manufacture of tool Co., Ltd., trade name " strength magnetic stirring apparatus RCX-1000D ") dipping is after 3 hours under stirring conditions, use Paulownia mountain funnel (manufactured by the production of Co., Ltd paulownia mountain, trade name " paulownia mountain funnel SB-60 ") and attraction clock (Co., Ltd's paulownia mountain system Manufactured by work, trade name " attracting clock VKB-200 "), pass through filter paper (manufactured by the production of Co., Ltd paulownia mountain, " No.50B ") decompression Filtering.Then, after the insoluble matter residue remained on filter paper being dried 3 hours at 120 DEG C with above-mentioned circulated air drying machine, The heat of water-soluble adhesive for cell is correctly calculated by following formula with the quality of above-mentioned quality meter measurement insoluble matter residue at 25 DEG C The gelling of resin after crosslinking divides rate.
Gelling divides rate (%)={ insoluble matter residue (g)/hard resin quality (g) } × 100
AM: acrylamide (manufacture of ケ ミ カ Le Co., Ltd., Mitsubishi, " 50% acrylamide ")
ATBS: acrylamide tert-butyl sulfonic acid (Toagosei Co., Ltd's manufacture, " ATBS ")
TBAA: N-tert-butyl acrylamide (manufacture of MCC Unitech Co., Ltd., " N tert butyl acrylamide ")
DMAA:N, N- dimethyl (methyl) acrylamide (manufacture of KJ ケ ミ カ Le ズ Co., Ltd., " DMAA ")
HEA: acrylic acid 2- hydroxyl ethyl ester (Osaka Organic Chemical Industry Co., Ltd.'s manufacture, " HEA ")
GLM: glycerin monomethyl acrylic ester (Japan Oil Co's manufacture, " Block レ ン マ ー GLM ")
PE-90: polyethylene glycol monomethacrylate (Japan Oil Co's manufacture, " Block レ ン マ ー PE-90 ")
PE-200: polyethylene glycol monomethacrylate (Japan Oil Co's manufacture, " Block レ ン マ ー PE-200 ")
AA: acrylic acid (Osaka Organic Chemical Industry Co., Ltd.'s manufacture, " 80% acrylic acid ")
AN: acrylonitrile (manufacture of ケ ミ カ Le Co., Ltd., Mitsubishi, " acrylonitrile ")
SMAS: Sodium methallyl sulfonate
Carbodiimides: carbodiimide compound (Nisshinbo ケ ミ カ Le Co., Ltd., " カ Le ボ ジ ラ イ ト V- 02”)
2. the manufacture of electrode slurry and battery manufacture and evaluation
Embodiment 2-1
Using commercially available rotation-revolution blender, (trade name " あ わ と り practices Taro ", シ ン キ ー (Co., Ltd.) are made Make), in the dedicated container of the blender, water-soluble poly (methyl) acryloyl containing hydroxyl that embodiment 1-1 is obtained The lithium ion battery of amine (A) is scaled 7 mass parts, D50 according to solid component with heat cross-linking binder aqueous solution as 5 μm of silicon 50 mass parts of particle and natural graphite (her vine black plumbing Co., Ltd. manufactures, trade name " Z-5F ") 50 mass parts are mixed It closes.Herein, ion exchange water is added, so that solid component concentration is become 40%, which is placed in above-mentioned blender.Then, (kneading) is kneaded after ten minutes in 2000rpm, is carried out de-bubble in 1 minute, is obtained electrode slurry.
Embodiment 2-2~embodiment 2-11, comparative example 2-1~comparative example 2-4
In addition to the composition in above-described embodiment 2-1 is changed to shown in table 2 form other than, it is other with embodiment 2- 1 same mode is operated, and slurry is prepared.
<calculating of rebound degree>
On the surface for the collector being made of copper foil, in such a way that the film thickness after drying is 25 μm equably by scraper method It is coated with obtained slurry, after 1 hour dry at 80 DEG C, handled 2 hours in 150 DEG C/heating under vacuum, obtains electrode.Then, Press process is carried out by roll squeezer so that the density of film (electrode active material layer) is 1.5g/cm3, thus obtain electrode.Make With obtained electrode according to following program making lithium half-cells, implements charge and discharge electrometric determination, calculate rebound degree.
<shed storage test of electrode slurry>
After viscosity (unit: mPas) with Brookfield viscometer measurement electrode slurry, stored in the baking oven for being warming up to 40 DEG C 3 days.After storage, viscosity is measured again with Brookfield viscometer, is calculated viscosity change with following formula, is evaluated with following evaluation criterions.
Viscosity change (%)=(viscosity of the electrode slurry after storage)/(viscosity of the electrode slurry before storage) × 100
A: less than 110%
B:110% or more, less than 120%
C:120% or more, less than 130%
D:130% or more
<assembling of lithium half-cell>
In the glove box replaced by argon, the material that above-mentioned electrode punching shaping is diameter 16mm will be loaded into test electricity The inside of liner (パ ッ キ Application) on the lower lid of the A1 in pond (manufacture of Japan, Co., Ltd ト system セ Le company).Then, it will rush It is cut into the diaphragm (CS TECH CO., LTD manufacture, the trade name " Selion that are formed by polypropylene perforated membrane of diameter 24mm P2010 ") it loads, it further injects into after electrolyte can enter air not, the material that metallic lithium foil punching shaping is 16mm is filled It carries.Then, in order to equably oppress electrode and lithium metal, the disk and leaf spring of SUS is placed, is finally placing the upper of SUS Gai Hou is equably tightened using nut.Electrolyte used herein is in ethylene carbonate/methyl ethyl carbonate=1/1 (quality Than) solvent in LiPF dissolved with the concentration of 1 mole/L6Solution.
<charge and discharge electrometric determination>
Lithium half-cell is placed in 25 DEG C of thermostat, is started to charge with constant current (0.1C), in voltage as 0.01V's Time point completes charging (cut-off).Then, start to discharge with constant current (0.1C), complete to put as the time point of 1.0V in voltage Electric (cut-off), electricity repeated 30 times of such charge and discharge.
In addition, " 1C " in said determination condition, which refers to, put within constant-current discharge 1 hour with the battery of certain capacitor The current value that electricity terminates.Such as " 0.1C " refers to that the current value for spending electric discharge in 10 hours to terminate, " 10C " refer to cost 0.1 hour Discharge the current value completed.
<measurement of rebound degree>
After charge and discharge cycles test is carried out 30 circulations at (25 DEG C) of room temperature, lithium half-cell is decomposed, electrode is measured Thickness.The rebound degree of electrode is found out by following formula.
Rebound degree={ (thickness of electrode-current collection body thickness after 30 circulations)/(thickness of electrode-current collection before charge and discharge Body thickness) } × 100-100 (%)
Table 2
As shown in Table 2, the electrode slurry that makes in the binder aqueous solution using embodiment is made by the electrode slurry In the evaluation of lithium half-cell, the evaluation of the storage-stable and rebound degree of electrode slurry is good.

Claims (10)

1. lithium ion battery heat cross-linking binder aqueous solution, the lithium ion battery heat cross-linking binder aqueous solution contains There is water-soluble poly (methyl) acrylamide (A) of hydroxyl,
The solidfied material gelling point rate of water-soluble poly (methyl) acrylamide (A) of the hydroxyl is 20% or more and is following The polymer of monomer group: relative to 100 moles of % of monomer group, the monomer group contain 30 moles of %-95 moles of % containing (first Base) compound (a) of acrylamido, 5 moles of %-50 moles of % hydroxyl (methyl) acrylate (b).
2. lithium ion battery as described in claim 1 heat cross-linking binder aqueous solution, wherein the hydroxyl (methyl) acrylate (b) is indicated by the following general formula (1):
General formula (1):
[changing 1]
In formula, R1Indicate hydrogen atom or methyl；
R2Indicate the alkylidene oxide of substituted or unsubstituted carbon number 1-5,
The polyoxyalkylene indicated by general formula (2),
General formula (2):
[changing 2]
In formula, integer of the q for 1-3, the integer that n is 1 or more,
[changing 3]
Or their combination.
3. containing lithium ion battery as claimed in claim 1 or 2 heat cross-linking binder aqueous solution and electrode active material (B) lithium ion battery electrode slurry.
4. lithium ion battery electrode slurry as described in claim 3, wherein relative to the electrode active material (B) 100 mass %, the water-soluble poly (methyl) of the hydroxyl contained in the lithium ion battery heat cross-linking binder aqueous solution Acrylamide (A) is 1 mass %-15 mass %.
5. the lithium ion battery electrode slurry as described in claim 3 or 4, wherein the electrode active material (B) is contained The silicon or silica of the carbon-coating covering of 5 mass % or more.
6. the manufacturing method of the lithium ion battery electrode slurry as described in any one of claim 3-5, the method includes The step of water-soluble poly (methyl) acrylamide (A) and electrode active material (B) of hydroxyl are mixed, wherein
The solidfied material gelling point rate of water-soluble poly (methyl) acrylamide (A) of the hydroxyl is 20% or more and is following The polymer of monomer group: relative to 100 moles of % of monomer group, the monomer group contain 30 moles of %-95 moles of % containing (first Base) compound (a) of acrylamido, 5 moles of %-50 moles of % hydroxyl (methyl) acrylate (b).
7. by the way that the lithium ion battery electrode slurry as described in any one of claim 3-5 to be coated on the current collector and make Lithium ion battery electrode obtained from it is dried.
8. lithium ion battery electrode as described in claim 7, wherein the collector is copper foil.
9. the lithium ion battery electrode as described in claim 7 or 8, wherein the lithium ion battery electrode by Drying steps at 80 DEG C -200 DEG C obtain.
10. including the lithium ion battery of lithium ion battery electrode as claimed in any one of claims 7-9.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN112421034A (en) * 2019-08-22 2021-02-26 荒川化学工业株式会社 Binder aqueous solution for lithium ion battery, slurry for lithium ion battery negative electrode, and lithium ion battery
CN112447973A (en) * 2019-09-05 2021-03-05 荒川化学工业株式会社 Aqueous binder solution for lithium ion battery electrode, slurry for lithium ion battery electrode, and lithium ion battery
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WO2024024949A1 (en) * 2022-07-29 2024-02-01 富士フイルム株式会社 Binder composition for secondary battery, composition for electrode, electrode sheet, secondary battery, manufacturing method for said electrode sheet, and manufacturing method for said secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080034219A (en) * 2006-10-16 2008-04-21 주식회사 엘지화학 Binder for secondary battery containing copolymer of polyester acrylate-based compound
CN102439769A (en) * 2009-04-03 2012-05-02 东洋油墨Sc控股株式会社 Binder composition for non-aqueous secondary battery electrode
CN105226291A (en) * 2015-10-27 2016-01-06 苏州宽温电子科技有限公司 A kind of environment-friendly water-based binding agent and preparation method thereof
CN106220779A (en) * 2016-08-17 2016-12-14 四川茵地乐科技有限公司 Acrylonitrile copolymer binder and the application in lithium ion battery thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013023654A (en) * 2011-07-25 2013-02-04 Showa Denko Kk Binder for carbon coat foil coating solution, carbon coat foil coating solution, carbon coat foil, electrode for lithium ion secondary battery, and lithium ion secondary battery
JP2015118908A (en) 2013-11-14 2015-06-25 Jsr株式会社 Binder composition for electricity storage device, slurry for electricity storage device, electricity storage device electrode, separator, and electricity storage device
JP2015106488A (en) 2013-11-29 2015-06-08 Jsr株式会社 Slurry for electricity storage device negative electrode and electricity storage device negative electrode, slurry for electricity storage device positive electrode and electricity storage device positive electrode, and electricity storage device
KR102283287B1 (en) 2013-12-25 2021-07-28 제온 코포레이션 Binder composition for lithium ion secondary battery, slurry composition for lithium ion secondary battery, method for manufacturing electrode for secondary battery, and lithium ion secondary battery
PL3154113T3 (en) 2014-06-04 2022-07-25 Zeon Corporation Binder composition for lithium ion secondary battery electrode-use, slurry composition for lithium ion secondary cell electrode-use, electroe for lithium secondary cell electrode-use, and lithium ion secondary cell
JP6855681B2 (en) 2015-03-13 2021-04-07 日本ゼオン株式会社 Binder composition for lithium ion secondary battery electrode, slurry composition for lithium ion secondary battery electrode, electrode for lithium ion secondary battery and lithium ion secondary battery
KR101953765B1 (en) * 2015-06-17 2019-06-12 주식회사 엘지화학 Binder Composition for Secondary Battery, and Electrode Employed with the Same, and Lithium Secondary Battery
WO2018008555A1 (en) 2016-07-07 2018-01-11 日本ゼオン株式会社 Binder composition for nonaqueous secondary battery electrodes, slurry composition for nonaqueous secondary battery electrodes, electrode for nonaqueous secondary batteries, and nonaqueous secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080034219A (en) * 2006-10-16 2008-04-21 주식회사 엘지화학 Binder for secondary battery containing copolymer of polyester acrylate-based compound
CN102439769A (en) * 2009-04-03 2012-05-02 东洋油墨Sc控股株式会社 Binder composition for non-aqueous secondary battery electrode
CN105226291A (en) * 2015-10-27 2016-01-06 苏州宽温电子科技有限公司 A kind of environment-friendly water-based binding agent and preparation method thereof
CN106220779A (en) * 2016-08-17 2016-12-14 四川茵地乐科技有限公司 Acrylonitrile copolymer binder and the application in lithium ion battery thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110444765A (en) * 2019-08-12 2019-11-12 苏州大学 Application of the melamine Cross-linked Polyvinylalcohol Gel in lithium battery silicium cathode material
CN110444765B (en) * 2019-08-12 2021-09-21 苏州大学 Application of melamine crosslinked polyvinyl alcohol hydrogel in lithium battery silicon negative electrode material
CN112421034A (en) * 2019-08-22 2021-02-26 荒川化学工业株式会社 Binder aqueous solution for lithium ion battery, slurry for lithium ion battery negative electrode, and lithium ion battery
CN112447973A (en) * 2019-09-05 2021-03-05 荒川化学工业株式会社 Aqueous binder solution for lithium ion battery electrode, slurry for lithium ion battery electrode, and lithium ion battery
WO2024020724A1 (en) * 2022-07-25 2024-02-01 宁德时代新能源科技股份有限公司 Electrode slurry, electrode sheet and manufacturing method therefor, secondary battery, and electrical device
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