WO2018068268A1 - 粘结剂及其电化学储能装置 - Google Patents

粘结剂及其电化学储能装置 Download PDF

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Publication number
WO2018068268A1
WO2018068268A1 PCT/CN2016/102020 CN2016102020W WO2018068268A1 WO 2018068268 A1 WO2018068268 A1 WO 2018068268A1 CN 2016102020 W CN2016102020 W CN 2016102020W WO 2018068268 A1 WO2018068268 A1 WO 2018068268A1
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WIPO (PCT)
Prior art keywords
group
reactive functional
substituted
diisocyanate
unsubstituted
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PCT/CN2016/102020
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English (en)
French (fr)
Inventor
钟泽
孙成栋
郑义
冯凌云
Original Assignee
宁德新能源科技有限公司
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Application filed by 宁德新能源科技有限公司 filed Critical 宁德新能源科技有限公司
Priority to PCT/CN2016/102020 priority Critical patent/WO2018068268A1/zh
Priority to CN201680078762.0A priority patent/CN108473663A/zh
Publication of WO2018068268A1 publication Critical patent/WO2018068268A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of secondary batteries, and in particular to a binder and an electrochemical energy storage device thereof.
  • Lithium-ion batteries have advantages such as high energy density and long cycle life, and are widely used in mobile phones, notebook computers, and digital products.
  • the lithium ion battery is composed of a positive electrode, a negative electrode, a separator and an electrolyte.
  • the positive electrode and the negative electrode are separated by a separator, encapsulated in an aluminum plastic film, and injected into a certain electrolyte to form a lithium ion battery through formation, aging, and the like.
  • the positive electrode active material is usually made of lithium cobaltate or nickel cobalt manganese, nickel cobalt aluminum ternary material, and the negative electrode active material is graphite.
  • the positive active material (lithium cobaltate) deintercalates lithium ions, causing a lattice change, and the material itself does not produce significant volume change; while in the negative electrode, graphite acts as an active material, and lithium ion is embedded during charging. Between the graphite layers, the pitch of the graphite layer is increased, the negative electrode tab is expanded, lithium ions are removed from the graphite layer during discharge, the pitch of the graphite layer is reduced, and the thickness of the negative electrode tab is reduced.
  • the anode graphite undergoes a cyclical process of volume expansion and contraction, and the bond between the graphite particles by the binder (usually a styrene-butadiene rubber emulsion) is gradually weakened or destroyed, and the negative pole piece is irreversible.
  • the cyclic expansion causes the negative pole piece to be ultra thick, the thickness of the lithium ion battery increases, and the active material also has a high risk of falling off, causing the lithium ion battery to be unusable or ineffective, and the ultra thick thickness of the battery will largely affect its performance.
  • controlling the expansion of the negative pole piece of the lithium ion battery in the cycle is a very important research direction.
  • the primary object of the present application is to propose a binder.
  • a second object of the present application is to provide an electrochemical energy storage device containing the binder.
  • the present application relates to a binder characterized in that the binder contains separated first component and second component,
  • the first component contains at least one compound having a first reactive functional group, and the first reactive functional group is selected from at least one of an epoxy group or an isocyanate group;
  • the second component contains at least one polymer having a second reactive functional group
  • the first reactive functional group has an activity of reacting with the second reactive functional group, and the first reactive functional group reacts with the second reactive functional group to form a chemical bond;
  • the compound having an epoxy group contains at least two epoxy groups.
  • the epoxy group-containing compound contains at least three epoxy groups.
  • the epoxy group-containing compound has an epoxy equivalent of from 50 to 1,000.
  • the epoxy group-containing compound has a molar mass of from 100 to 10,000 g/mol.
  • the compound having an isocyanate group contains at least two isocyanate groups.
  • the compound having an isocyanate group has a molar mass of from 100 to 5000 g/mol.
  • the compound having an epoxy group is selected from the group consisting of:
  • the structural formula of the compound having an epoxy group is as follows:
  • R 11, R 12, R 13, R 14 are each independently selected from substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted alkenyl C 2 ⁇ 20 alkylene group;
  • R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 , R 4 are each independently selected from substituted or unsubstituted C 1-20 alkylene, substituted or unsubstituted alkenyl C 2 ⁇ 20 alkylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, a substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group and an acyl group At least two linked substituents;
  • the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen, a C 1-6 linear or branched alkyl group.
  • the epoxy group-containing compound is selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, pentaerythritol glycidyl ether, 1,4-butane Glycidyl ether, propylene glycol glycidyl ether, glycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, 4,4'-diaminodiphenylmethane
  • Glycidyl epoxy triglycidyl p-aminophenol, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, tetraglycidyl-1,3-bis(aminomethylcyclohexane) Alkane, 9,9-bis[(2,3-epoxypropoxy)phenyl]anthracene, 1,4-
  • the structural formula of the compound having an isocyanate group is as follows:
  • R 5 is selected from substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted C 2 ⁇ 20 alkenylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, substituted by a substituted or unsubstituted alkylene of C 1 ⁇ 20 alkyl group, a substituted or unsubstituted C 6 ⁇ 26 are connected in at least two substituent groups of the arylene group and an acyl group;
  • the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen, a C 1-6 linear or branched alkyl group.
  • the compound having an isocyanate group is selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and dimethylbiphenyl diisocyanate.
  • the second reactive functional group is selected from at least one of a hydroxyl group, a carboxyl group, and -NHR 1 , and R 1 is selected from H, a substituted or unsubstituted hydrocarbon group, and the substituent is selected from a halogen.
  • the polymer having the second reactive functional group is at least one selected from the group consisting of a cellulose ether polymer, a polyacrylamide polymer, a polyvinyl alcohol polymer, and a polyacrylic polymer.
  • the polymer having a second reactive functional group is selected from the group consisting of sodium carboxymethyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl fiber. , methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, benzyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, phenyl cellulose, polyacrylamide, polymethyl At least one of acrylamide, polyvinyl alcohol, and sodium alginate.
  • the binder further comprises a separate third component selected from the group consisting of emulsion binders.
  • the emulsion binder may be styrene-acrylic rubber or a derivative thereof, styrene-butadiene rubber or a derivative thereof, pure propylene rubber or a derivative thereof, nitrile rubber or a derivative thereof, chloroprene rubber or a derivative thereof At least one of them.
  • the present application relates to an electrochemical energy storage device comprising a positive electrode tab, a negative electrode tab, an electrolyte and a separator, at least one of the positive electrode tab, the negative electrode tab and the separator.
  • the content of the first component in the negative electrode tab is 0.01% to 2%, and the content of the second component in the negative electrode tab is 0.1% to 3%. .
  • the present application utilizes the chemical reactivity between the first reactive functional group and the second reactive functional group to form a chemical bond by reacting the epoxy group or the isocyanate group with the polymer under heating conditions to produce a three-dimensional crosslinked structure, which is far in strength. It is higher than the ordinary physical bond, and is especially suitable for the preparation of the positive electrode tab and the negative electrode tab in the secondary battery, which can improve the bonding force and cohesion of the pole piece.
  • the adhesive of the present application when used for the preparation of the negative electrode tab, under the premise of ensuring the electrical properties of the secondary battery, the irreversible expansion of the negative electrode tab of the secondary battery during the manufacturing process can be significantly reduced, and the battery is lowered. Thickness, increase energy density, reduce irreversible expansion during cycling, and improve cycle life.
  • the present application relates to a binder comprising a separate first component and a second component, i.e., the first component and the second component are each individually packaged and mixed at the time of use.
  • the first component of the present application contains at least one compound having a first reactive functional group, the first reactive functional group is selected from at least one of an epoxy group or an isocyanate group; and the second component contains at least one of a polymer of a second reactive functional group; the first reactive functional group has an activity of reacting with the second reactive functional group, and the first reactive functional group reacts with the second reactive functional group to form a chemical bond to produce a three-dimensional crosslinked structure, and is particularly suitable For the bonding of particulate matter.
  • the compound having an epoxy group is a polyepoxy group compound containing at least two epoxy groups, thereby forming a three-dimensional network crosslinked structure.
  • the epoxy group is located at both ends of the molecular structure of the compound, that is, when the compound having an epoxy group is a long-chain compound, both ends of the long-chain molecule are bonded with an epoxy group.
  • the polyepoxy group compound contains at least three epoxy groups, preferably 2 to 6 epoxy groups, and more preferably 2 to 5 rings. Oxygen group.
  • the structural formula is as shown in Formulas 1 to 4. When the number of epoxy groups is increased, the crosslinking reaction efficiency is higher.
  • the number of epoxy groups of the polyepoxy group compound in the present application is related to the molecular weight and epoxy equivalent of the polyepoxy group compound selected in the present application.
  • the molar mass of the polyepoxy group compound of the present application is preferably from 100 to 10000 g/mol, and the polyepoxy group in the molecular weight range is preferred. It is difficult to introduce more than 6 epoxy groups in the structure of the compound.
  • the epoxy equivalent of the polyepoxy group compound of the present application is preferably from 50 to 1000.
  • the epoxy compound having a higher molecular weight there may be more than 6 epoxy groups in the structure, but the epoxy equivalent is further caused to be excessively high.
  • the cross-linking reaction efficiency is rather low.
  • the polyepoxy group compound has an epoxy equivalent of from 50 to 1,000.
  • epoxy equivalent means the number of grams of epoxy resin containing one equivalent of epoxy group, in units of grams per equivalent. If the epoxy equivalent is too high, the crosslinking reaction efficiency is lowered.
  • the epoxy equivalent of the polyepoxy group compound is more preferably from 80 to 800.
  • the polyepoxy group compound has a molar mass of from 100 to 10,000 g/mol. If the molecular weight of the compound is too large, the viscosity is too large and it is difficult to disperse; if the molecular weight is too small, it is difficult to introduce two or more epoxy groups.
  • the molar mass of the polyepoxy group compound is further preferably from 200 to 3,000 g/mol.
  • the mass ratio of the first component to the second component is 1:1 to 200, preferably 1:2. 50.
  • the compound having an isocyanate group contains at least Two isocyanate groups. More preferably, it contains 2 to 6 isocyanate groups.
  • the isocyanate group is located at both ends of the molecular structure of the compound, that is, when the compound having an isocyanate group is a long-chain compound, the long-chain molecule is bonded to the isocyanate group at both ends thereof.
  • the compound having an isocyanate group has a molar mass of from 100 to 5000 g/mol.
  • the mass ratio of the first component to the second component is 1:1 to 200, preferably 1:2 to 50. .
  • the reaction temperature of the first reactive functional group and the second reactive functional group is 60 to 180 °C. This application requires heating to form a bond and is therefore easier to control.
  • the polyepoxy group compound may be selected from the group consisting of glycidyl ether type, glycidyl ester type or glycidylamine type, wherein the functional group in the glycidyl ether type is as shown in formula II.
  • the functional group in the glycidyl ester type is as shown in Formula III, and the functional group in the glycidylamine type is as shown in Formula IV:
  • the polyepoxy group compound may be selected from an aliphatic epoxy resin, and the specific structural formula is as shown in Formula IA to Formula ID:
  • R 11, R 12, R 13, R 14 are each independently selected from substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted alkenyl C 2 ⁇ 20 alkylene group; substituents selected from hydroxy , carboxyl, halogen.
  • R 11 , R 12 , R 13 and R 14 are intermediate linking groups, and the epoxy groups are located on the same carbon atom or different carbon atoms of the intermediate linking group, preferably on different carbon atoms.
  • R 11, R 12, R 13, R 14 are each independently selected from substituted or unsubstituted C 6 ⁇ 20 alkylene group, a substituted or unsubstituted C 6 ⁇ 20 alkenylene.
  • the polyepoxy group compound may be selected from the group consisting of glycidyl ether type epoxy compounds, and the specific structural formula is as shown in Formula IIA to Formula IID:
  • the polyepoxy group compound may be selected from the group consisting of glycidyl ester type epoxy compounds, and the specific structural formula is as shown in Formula IIIA to Formula IIID:
  • the polyepoxy group compound may be selected from a glycidyl ester type epoxy compound, and the specific structural formula is as shown in Formula IVA:
  • R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 , R 4 are each independently selected from substituted or unsubstituted C 1-20 alkylene groups. , a substituted or unsubstituted C 2 ⁇ 20 alkenylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, a substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted C 6 ⁇ 26 a substituent in which at least two of an arylene group and an acyl group are bonded;
  • the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen, a C 1-6 linear or branched alkyl group.
  • R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 , R 4 are each independently selected from substituted or unsubstituted C 6-20 alkylene groups, substituted or unsubstituted C 6 ⁇ 20 alkenylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, a substituted or unsubstituted C 1 ⁇ 18 alkylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene A substituent formed by linking at least two of the acyl groups.
  • R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 , R 4 are intermediate linking groups, and the epoxy group is located at the same carbon atom or different from the intermediate linking group. On the carbon atom, preferably, on a different carbon atom.
  • the polyepoxy group compound is selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, pentaerythritol glycidyl ether, 1, 4-butanediol glycidyl ether, propylene glycol glycidyl ether, glycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, 4,4'-diamino Diphenylmethane tetraglycidyl epoxy, triglycidyl p-aminophenol, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, tetraglycidyl-1,3-bis(ammonia) Methylcyclohexane), 9,9-bis[(2,3-epoxy)
  • polyepoxy group compound of the present application may also be selected from:
  • the polyfunctional epoxy compound in the present application can be obtained by reacting NaOH and epichlorohydrin under certain conditions through the corresponding small molecule precursor, and the small molecule precursor can be selected as: bisphenol A, bisphenol F, Bisphenol S, pentaerythritol, 1,4-butanediol, propylene glycol, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydroortho Phthalic anhydride, 4,4'-diaminodiphenylmethane, p-aminophenol, 1,3-dimethylamidocyclohexane, 1,3-diaminomethylcyclohexane, 9,9-bis ( 4-hydroxyphenyl)indole 9,9-diphenylanthracene, 1,4-cyclohexanedimethanol.
  • the small molecule precursor can be selected as
  • the structural formula of the compound having an isocyanate group is as follows:
  • R 5 is selected from substituted or unsubstituted C 1 ⁇ 20 alkylene group, a substituted or unsubstituted C 2 ⁇ 20 alkenylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, substituted by a substituted or unsubstituted alkylene of C 1 ⁇ 20 alkyl group, a substituted or unsubstituted C 6 ⁇ 26 are connected in at least two substituent groups of the arylene group and an acyl group;
  • the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen, a C 1-6 linear or branched alkyl group.
  • R 5 is selected from substituted or unsubstituted C 6 ⁇ 20 alkylene group, a substituted or unsubstituted C 6 ⁇ 20 alkenylene group, a substituted or unsubstituted C 6 ⁇ 26 arylene group, a substituted or unsubstituted substituted C 1 ⁇ 18 alkylene group, a substituted or unsubstituted C 6 ⁇ 26 are connected in at least two substituent groups of the arylene group and an acyl group;
  • the substituent is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen, a C 1-6 linear or branched alkyl group.
  • R 5 is an intermediate linking group, and the epoxy group is located on the same carbon atom or a different carbon atom of the intermediate linking group, preferably on a different carbon atom.
  • the first reactive functional group is selected from the group consisting of isocyanate groups
  • the compound having an isocyanate group is selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate.
  • Acid ester 1,5-naphthalene diisocyanate, dimethylbiphenyl diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexan Isocyanate, benzodimethyl diisocyanate, tetramethylbenzene dimethylene diisocyanate, hydrogenated benzene dimethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1, At least one of 4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1,4-benzene diisocyanate, and norbornane diisocyanate.
  • the alkylene group having 1 to 20 carbon atoms may be a chain alkylene group or a cycloalkylene group, and the hydrogen group on the ring of the cycloalkylene group may be substituted by an alkyl group.
  • the lower limit of the number of carbon atoms in the alkyl group is preferably 2, 3, 4, 5, and the preferred upper limit is 3, 4, 5, 6, 8, 10, 12, 14, 16, 18.
  • an alkylene group having 1 to 18 carbon atoms is selected, and more preferably, a chain alkylene group having 1 to 12 carbon atoms and a cycloalkylene group having 3 to 8 carbon atoms are selected.
  • a chain alkylene group having 1 to 8 carbon atoms and a cycloalkylene group having 5 to 7 carbon atoms are selected.
  • the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, an anthranylene group, and an anthranylene group.
  • the alkenylene group having 2 to 20 carbon atoms may be a cyclic alkenylene group or a chain alkenylene group. Further, the number of double bonds in the alkenylene group is preferably one.
  • the lower limit of the number of carbon atoms in the alkenylene group is preferably 3, 4, 5, and the preferred upper limit is 3, 4, 5, 6, 8, 10, 12, 14, 16, 18.
  • an alkenylene group having 2 to 18 carbon atoms is selected, and an alkenylene group having 2 to 12 carbon atoms is more preferably selected, and an alkenyl group having 2 to 8 carbon atoms is more preferably selected.
  • alkenyl group examples include a vinylidene group, an allylene group, a pentenylene group, a cyclohexylene group, a cyclohexylene group, and a cyclooctene group.
  • An arylene group having 6 to 26 carbon atoms such as a phenylene group, a phenylene group, an aryl group containing at least one phenylene group such as a biphenylylene group, a fused ring aromatic hydrocarbon group such as a naphthalene group, an anthracene, or a sub
  • the phenanthrene and the fused aromatic hydrocarbon group may be substituted by an alkyl group or an alkenyl group.
  • an arylene group having 6 to 22 carbon atoms is selected, and more preferably, an arylene group having 6 to 16 carbon atoms is selected, and more preferably, an arylene group having 6 to 12 carbon atoms is selected. .
  • aryl group examples include a phenylene group, a benzylidene group, a biphenyl group, a p-terphenylene group, an o-paraphenylene group, and a m-phenylene group.
  • the second reactive functional group is selected from at least one of a hydroxyl group, a carboxyl group, and -NHR 1 , and R 1 is selected from H, a substituted or unsubstituted hydrocarbon group, and the substituent is selected from a halogen.
  • At least one selected from the group consisting of a cellulose ether polymer, a polyacrylamide polymer, a polyvinyl alcohol polymer, and a polyacrylic polymer has a polymer having a second reactive functional group.
  • the polymer having the second reactive functional group is selected from the group consisting of sodium carboxymethyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, Hydroxypropyl methylcellulose, methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, benzyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, phenyl cellulose, At least one of polyacrylamide, polymethacrylamide, polyvinyl alcohol, and sodium alginate.
  • the adhesive further comprises a separate third component selected from the group consisting of emulsion binders.
  • the first reactive functional group can further chemically react with the third component to form a three-dimensional crosslinked structure, which improves the bond strength and cohesion of the pole piece.
  • the mass ratio of the first component, the second component to the third component is from 1:1 to 200:1 to 200, preferably from 1:2 to 50: 2 to 50.
  • the mass ratio of the first component, the second component to the third component is 1:1 to 200:1 to 200, preferably 1:2 to 50:2 to 50. .
  • the emulsion binder may be styrene-acrylic rubber or a derivative thereof, styrene-butadiene rubber or a derivative thereof, pure propylene rubber or a derivative thereof, nitrile rubber or a derivative thereof, chlorine At least one of butyl rubber or a derivative thereof.
  • the independent first component and the second component are added to the water in proportion to obtain a binder slurry, and the slurry is applied to the portion to be bonded. Bonding between the two components can also be used for the bonding of particulate materials. After applying the slurry, the object to be bonded is heated to 60-180 ° C for a period of 1 to 120 minutes, thereby reacting the epoxy group or the isocyanate group with the second reactive functional group under heating to form a chemical bond. Bonding.
  • the present application also relates to the application of the adhesive, specifically, to the field of secondary batteries; further preferably, it is used as a binder of a secondary battery pole piece, and further preferably, it is used as a secondary battery negative electrode piece Adhesive.
  • the present application also relates to an electrochemical energy storage device comprising a positive electrode tab, a negative electrode tab, an electrolyte and a separator, at least one of the positive pole tab, the negative pole tab and the separator having the bond of the present application Agent.
  • the binder of the present application can be used for preparation of an active material layer in a positive electrode tab/negative electrode tab, and a positive electrode active material/negative electrode active material is prepared as a slurry coated on a current collector, and dried to obtain a positive electrode tab/negative electrode sheet.
  • the adhesive of the present application can also be applied to a separator for bonding a positive electrode tab to a separator or for bonding a negative electrode tab to a separator.
  • the binder of the present application is particularly suitable for the preparation of a negative electrode pole piece.
  • the graphite is added to the water for stirring, and the binder of the present application is separately added during the stirring process.
  • the first component and the second component are chemically reacted with the second component having the second reactive functional group to form a three-dimensional network intersection by heating in the pole piece drying process Joint structure.
  • the irreversible expansion of the negative electrode piece of the secondary battery during the manufacturing process can be significantly reduced, the thickness of the battery is reduced, the energy density is increased, the irreversible expansion during the cycle is reduced, and the cycle life is improved.
  • the first component is a compound having at least two epoxy groups, and if the first component is a compound having only one epoxy group, the reaction cannot be produced after the reaction.
  • the crosslinked structure cannot meet the requirements for adhesives in the preparation of the negative electrode sheets.
  • a polyfunctional epoxy compound containing at least three epoxy groups is selected as the first component for the negative electrode tab adhesive, and the crosslinking reaction is more efficient, and the expansion and reduction of the negative electrode tab are suppressed. The effect of cyclic expansion is better.
  • the first reactive functional group is an isocyanate group
  • the first component is a compound having at least two isocyanate groups, and the crosslinking reaction is more efficient, and the expansion of the negative electrode sheet is suppressed and reduced. The effect of small circulation expansion is better.
  • the molecular weight thereof ranges from 100 to 10000 (g/mol), and in this range, the polyepoxy group compound It has low viscosity and good dispersibility in water, so it can be uniformly dispersed in the aqueous negative electrode slurry.
  • the first component has a mass percentage of 0.01% to 2% in the negative electrode tab
  • the second component has a mass percentage of 0.1 to 3 in the negative electrode tab. %.
  • the negative electrode tab further contains a third component, the third component is an emulsion binder, and the surface of the emulsion binder generally has an aqueous -COOH
  • the first reactive functional group can further chemically react with the third component to form a three-dimensional crosslinked structure, which improves the bonding force and cohesion of the pole piece.
  • the second component may be selected from the group consisting of cellulose ether polymers, and the structure of the cellulose ether polymer contains -COOH and -OH, and the first reactive functional group may simultaneously -COOH reacts with -OH to form a three-dimensional crosslink.
  • the second component is selected from the group consisting of a cellulose ether polymer, and an emulsion binder is simultaneously added as a third component, and the emulsion is bonded.
  • the surface of the agent usually has an aqueous group such as -COOH, and the first reactive functional group further chemically reacts with the second component and the third component to further improve the adhesion and cohesion of the pole piece.
  • This embodiment provides an adhesive whose composition is as shown in Table 1:
  • the separated first component, second component and third component are mixed in proportion and used.
  • the mass ratio of the first component to the second component is 1:1 to 200, preferably 1:2 to 50; the mass ratio of the first component, the second component to the third component is 1:1 to 200. : 1 to 200, preferably 1:2 to 50:2 to 50.
  • the components After soaking the electrolyte: the components are uniformly mixed, uniformly coated on the steel plate, heated and dried, baked at 100 ° C for 1 hour, and immersed in the electrolyte (same as the electrolyte in the preparation process of the lithium ion battery) It is immersed in a dry environment (relative humidity ⁇ 5%) at room temperature for 24 hours, then taken out to naturally evaporate in a dry environment, and the organic solvent on the surface of the negative electrode sheet is volatilized, and the adhesion of the negative electrode sheet is tested.
  • the test method and the calculation method of the cohesive force are the same as above.
  • Adhesion force before soaking the electrolyte (N/m) Adhesion force after soaking electrolyte (N/m) 1 21.3 3.7 2 24.6 4.1 3 88.3 31.9 4 82.5 29.1 5 91.6 33.5 6 77.7 28.2 7 84.4 32.7 8 88.8 30.6 9 91.7 39.5 10 52.4 18.3 11 82.5 31.7 12 79.8 30.2 13 92.6 38.8 14 81.3 31.0 15 85.9 33.5 16 78.2 28.1
  • This embodiment provides an adhesive whose composition is as shown in Table 3:
  • the separated first component, second component and third component are mixed in proportion and used.
  • Adhesion force before soaking the electrolyte (N/m) Adhesion force after soaking electrolyte (N/m) 1 19.2 4.1 2 21.8 4.5 3 67.0 27.4 4 63.2 25.2 5 69.2 28.6 6 59.9 24.6 7 64.4 28.0 8 67.4 26.4 9 69.3 33.0 10 42.4 16.8
  • the present embodiment provides a negative electrode tab using a binder of the present application and a lithium ion battery thereof, the lithium ion battery including a positive electrode tab, a negative electrode tab, a separator, and an electrolyte, and the positive electrode tab includes a cathode current collector and a cathode active material layer .
  • the negative electrode sheet included a negative electrode current collector and a negative electrode active material layer, and the negative electrode current collector was a copper foil having a thickness of 8 ⁇ m. According to the mass fraction, the composition of the active material layer in the negative electrode tab is as shown in Table 5:
  • the negative electrode conductive agent is acetylene black
  • the type of styrene-butadiene rubber emulsion is Japan Zeon, BM400.
  • the composition of the active material layer in the positive electrode tab of the lithium ion battery of the present embodiment is:
  • the positive active material is LiCoO 2 , and the content is 96.0%;
  • the positive electrode binder is polyvinylidene fluoride, and has a molecular weight of 600,000 to 1,200,000 and a content of 2.0%;
  • the positive electrode conductive agent content is 2.0%
  • the positive electrode current collector was an aluminum foil and had a thickness of 12 ⁇ m.
  • the separator is a polyethylene separator with a thickness of 10 ⁇ m.
  • the electrolyte includes an organic solvent and a lithium salt.
  • the organic solvent is a mixture of diethyl carbonate, dimethyl carbonate and ethylene carbonate.
  • the volume ratio of the three solvents is 1:1:1
  • the lithium salt is LiPF 6
  • the concentration is 1 mol. /L.
  • positive electrode tab 96.0% lithium cobalt oxide LiCoO 2 , 2.0% polyvinylidene fluoride PVdF, 2.0% positive electrode conductive agent was added to NMP, stirred evenly, coated on aluminum foil, dried, rolled, and divided. Cutting and welding the positive electrode tab to obtain a positive electrode sheet;
  • the preparation of the negative pole piece according to the components shown in Table 5, added to the distilled water to stir evenly, coated on the copper foil, after drying, rolling, slitting, welding the negative electrode tab to obtain the negative pole piece;
  • the positive electrode piece, the negative electrode piece and the separator are wound into a battery core, the battery core is placed in an aluminum plastic film, baked and water is removed, and then the electrolyte is injected to form and age the battery core.
  • the corresponding lithium ion batteries B1 to B7 are obtained.
  • a negative electrode tab was prepared in the same manner as in Example 3 except that the composition of the negative electrode tab was as shown in Table 6:
  • a lithium ion battery was prepared in accordance with the method of Example 3 to obtain corresponding lithium ion batteries BD1 to BD4.
  • a negative electrode tab was prepared in the same manner as in Example 3 except that the composition of the negative electrode tab was as shown in Table 7:
  • Shell 1009 epoxy resin has an epoxy equivalent of about 3000
  • Shell 1007 epoxy tree The epoxy equivalent of the grease is about 2,000.
  • a lithium ion battery was prepared in accordance with the method of Example 3 to obtain corresponding lithium ion batteries BD5 to BD8.
  • Pole piece thickness Take the negative pole piece of lithium battery in different states, and test the thickness of the pole piece with a micrometer (Mitutoyo, Japan, model 293). The number of test points per pole piece is not less than 10, and the average value is taken as the thickness of the pole piece. The data is shown in Table 8;
  • the thickness of the active material layer when semi-filled thickness of the semi-charged pole piece - the thickness of the current collector
  • Thickness of active material layer after cold pressing thickness of pole piece after cold pressing - thickness of current collector.
  • Battery thickness The battery thickness is tested with a micrometer. Each battery is tested with 3 sets of data. The average value is taken as the battery thickness value. The test data is shown in Table 9.
  • the second component can only function to thicken and stabilize the slurry, while the third component acts as a bonding agent and cannot be combined with the negative electrode.
  • the active material completes three-dimensional cross-linking, so the rebound of the negative electrode after cold pressing and cycling can not be suppressed.
  • the thickness of the pole piece and the battery in the comparative example are significantly thickened. After disassembling, it is found that the negative electrode piece occurs. With irreversible expansion, the electrical performance of lithium-ion batteries cannot be guaranteed.
  • the results of the examples of the present application confirmed that the first component in the adhesive of the present application has a relatively good effect when it is added at about 0.2%, and the overall performance has an advantage.
  • the irreversible cyclic expansion of the battery can also be significantly reduced, which is beneficial to improve the cycle life of the battery.
  • the addition amount is too low, a stable three-dimensional crosslinked structure cannot be formed; and when the addition amount is too large, there is no further increase in the thickness improvement, and the energy density of the negative electrode sheet is also affected.
  • the preparation of the negative electrode tab was carried out by using the other binders in Example 1 and Example 2.
  • the performance of the obtained lithium ion battery was similar to that of the experimental example, and is not limited herein.

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Abstract

一种粘结剂及其电化学储能装置。粘结剂含有分离的第一组分和第二组分，第一组分中含有至少一种具有第一反应官能团的化合物，第一反应官能团选自环氧基团或异氰酸酯基团中的至少一种，第二组分中含有至少一种具有第二反应官能团的聚合物，第一反应官能团与第二反应官能团反应形成化学键。利用第一反应官能团与第二反应官能团之间的化学反应性，产生三维交联结构，其强度远远高于普通的物理粘结，特别适用于二次电池中极片的制备，可提高极片粘结力和内聚力，降低极片冷压后的反弹和循环过程中的膨胀，提高能量密度。

Description

[根据细则37.2由ISA制定的发明名称]　粘结剂及其电化学储能装置 技术领域
本申请涉及二次电池领域，具体讲，涉及一种粘结剂及其电化学储能装置。
背景技术
锂离子电池具有高能量密度、长循环寿命等优点，目前已广泛用于移动电话、笔记本电脑、数码产品中。锂离子电池由正极、负极、隔离膜和电解液构成，其中正极、负极中以隔离膜隔开，封装于铝塑膜中，注入一定电解液后通过化成、老化等过程，制作成锂离子电池。其中正极活性材料常采用钴酸锂或镍钴锰、镍钴铝三元材料，负极活性材料为石墨。
在锂离子电池使用过程中，正极活性材料(钴酸锂)脱嵌锂离子，产生晶格变化，材料本身不会产生明显的体积变化；而在负极，石墨作为活性材料，充电时锂离子嵌入到石墨层之间，使得石墨层间距变大，负极极片膨胀，放电时锂离子从石墨层中脱出，石墨层间距变小，负极极片厚度减小。在电池循环过程中，负极石墨在不断发生体积膨胀和收缩的循环过程，石墨颗粒之间由粘结剂(通常是丁苯橡胶乳液)的粘结会逐渐弱化或被破坏，负极极片产生不可逆的循环膨胀，导致负极极片超厚，锂离子电池厚度增加，活性材料也有较高的脱落风险，造成锂离子电池无法使用或者失效，电池超厚也会在很大程度上影响其使用性能，尤其对于小型电子设备，如手机、笔记本电脑等。因此，控制锂离子电池在循环中的负极极片膨胀，是非常重要的研究方向。
鉴于此，特提出本申请。
发明内容
本申请的首要发明目的在于提出一种粘结剂。
本申请的第二发明目的在于提出一种含有该粘结剂的电化学储能装置。
为了完成本申请的目的，采用的技术方案为：
本申请涉及一种粘结剂，其特征在于，所述粘结剂含有分离的第一组分和第二组分，
所述第一组分中含有至少一种具有第一反应官能团的化合物，所述第一反应官能团选自环氧基团或异氰酸酯基团中的至少一种；
所述第二组分中含有至少一种具有第二反应官能团的聚合物；
所述第一反应官能团具有与所述第二反应官能团反应的活性，且所述第一反应官能团与所述第二反应官能团反应形成化学键；
当所述第一反应官能团选自环氧基团时，具有环氧基团的化合物中含有至少两个环氧基团。
优选的，所述具有环氧基团的化合物中含有至少三个环氧基团。
优选的，所述具有环氧基团的化合物的环氧当量为50～1000。
优选的，所述具有环氧基团的化合物的摩尔质量为100～10000g/mol。
优选的，所述具有异氰酸酯基团的化合物含有至少两个异氰酸酯基团。
优选的，所述具有异氰酸酯基团的化合物的摩尔质量为100～5000g/mol。
优选的，所述具有环氧基团的化合物选自具有以下基团的化合物：
Figure PCTCN2016102020-appb-000001
优选的，所述具有环氧基团的化合物的结构式如下所示：
Figure PCTCN2016102020-appb-000002
Figure PCTCN2016102020-appb-000003
其中，R11、R12、R13、R14各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基；
R21、R22、R23、R24、R31、R32、R33、R34、R4各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
优选的，所述带有环氧基团的化合物选自双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、季戊四醇缩水甘油醚、1,4-丁二醇缩水甘油醚、丙二醇缩水甘油醚、苯二甲酸缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、六氢邻苯二甲酸二缩水甘油酯、4,4’-二氨基二苯甲烷四缩水甘油基环氧、三缩水甘油基对氨基苯酚、1,3-双(N,N-二缩水甘油氨甲基)环己烷、四缩水甘油-1,3-双(氨甲基环己烷)、9,9-二[(2,3-环氧丙氧基)苯基]芴、1,4-环己烷二甲醇二缩水甘油醚、四缩水甘油基-4,4’-二氨基二苯醚、四缩水甘油基-3,4’-二氨基二苯醚中的至少一种。
优选的，所述第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物的结构式如下所示：
Figure PCTCN2016102020-appb-000004
其中，R5选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、 取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
优选的，所述第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、二甲基联苯二异氰酸酯、六亚甲基二异氰酸酯、2,2,4-三甲基己二异氰酸酯、2,4,4-三甲基己二异氰酸酯、苯二甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基环己烷二异氰酸酯、1,4苯二异氰酸酯、降冰片烷二异氰酸酯中的至少一种。
优选的，所述第二反应官能团选自羟基、羧基、-NHR1中至少一种，R1选自H、取代或未取代的烃基，取代基选自卤素。
优选的，所述具有第二反应官能团的聚合物的选自纤维素醚聚合物、聚丙烯酰胺聚合物、聚乙烯醇聚合物、聚丙烯酸类聚合物中的至少一种。
优选的，所述具有第二反应官能团的聚合物选自羧甲基纤维素钠、羟乙基纤维素、羧甲基羟乙基纤维素钠、羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素、羟乙基甲基纤维素、乙基纤维素、苄基纤维素、氰乙基纤维素、苄基氰乙基纤维素、苯基纤维素、聚丙烯酰胺、聚甲基丙烯酰胺、聚乙烯醇、海藻酸钠中的至少一种。
优选的，所述粘合剂中还含有分离的第三组分，所述第三组分选自乳液粘结剂。
优选的，所述乳液粘结剂可以是苯丙橡胶或其衍生物、丁苯橡胶或其衍生物、纯丙橡胶或其衍生物、丁腈橡胶或其衍生物、氯丁橡胶或其衍生物中的至少一种。
本申请涉及一种电化学储能装置，含有正极极片、负极极片、电解液和隔离膜，所述正极极片、负极极片和隔离膜中至少一种本申请的粘结剂。
优选的，所述第一组分在所述负极极片中的质量百分比含量为0.01％～2％，所述第二组分在所述负极极片中的质量百分比含量为0.1％～3％。
本申请的技术方案至少具有以下有益的效果：
本申请利用第一反应官能团与第二反应官能团之间的化学反应性，利用环氧基团或异氰酸酯基团与聚合物在加热条件下发生反应形成化学键，产生三维交联结构，其强度远远高于普通的物理粘结，特别适用于二次电池中正极极片和负极极片的制备，可提高极片粘结力和内聚力。
特别是当本申请的粘合剂在用于负极极片的制备时，在保证二次电池的电性能的前提下，能明显降低二次电池在制作过程中的负极极片不可逆膨胀，降低电池厚度，提高能量密度，减小循环过程中不可逆膨胀，提高循环寿命。
下面结合具体实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
具体实施方式
本申请涉及一种粘结剂，含有分离的第一组分和第二组分，即第一组分和第二组分各自分别独自包装，在使用时混合。本申请的第一组分中含有至少一种具有第一反应官能团的化合物，第一反应官能团选自环氧基团或异氰酸酯基团中的至少一种；第二组分中含有至少一种具有第二反应官能团的聚合物；第一反应官能团具有与第二反应官能团反应的活性，且所述第一反应官能团与所述第二反应官能团反应形成化学键，以产生三维交联结构，并尤其适用于颗粒状物质的粘结。
当第一反应官能团选自环氧基团时，具有环氧基团的化合物为含有至少两个环氧基团的多环氧基团化合物，从而可形成三维网状交联结构。优选的，环氧基团位于化合物分子结构的两端，即当具有环氧基团的化合物为一长链化合物时，长链分子的两端均连接有环氧基团。
作为本申请粘结剂的一种改进，多环氧基团化合物中含有至少三个环氧基团，优选的，含有2～6个环氧基团，进一步优选的，含有2～5个环氧基团。其结构通式如式1～式4所示。当环氧基团的个数越多，交联反应效率更高。本申请中多环氧基团化合物的环氧基团的个数与本申请选用的多环氧基团化合物的分子量和环氧当量有关。本申请多环氧基团化合物的摩尔质量选用100～10000g/mol为宜，在该分子量范围内的多环氧基团 化合物的结构中难以引入6个以上环氧基团。本申请多环氧基团化合物的环氧当量选用50～1000为宜，对于分子量更高的环氧化合物，其结构中可能有超出6个环氧基团，但会进一步引发环氧当量过高，交联反应效率反而较低。
Figure PCTCN2016102020-appb-000005
作为本申请粘结剂的一种改进，多环氧基团化合物的环氧当量为50～1000。在本申请中，环氧当量是指含有一当量环氧基的环氧树脂克数，单位为：克/当量。如环氧当量过高，则交联反应效率会降低。多环氧基团化合物的环氧当量进一步优选为80～800。
作为本申请粘结剂的一种改进，多环氧基团化合物的摩尔质量为100～10000g/mol。如果化合物的分子量过大，则粘度过大，不易分散；如分子量过小，难以引入2个以上环氧基团。多环氧基团化合物的摩尔质量进一步优选200～3000g/mol。
作为本申请粘结剂的一种改进，当第一组分为多环氧基团化合物时，第一组分与第二组分的质量比为1：1～200，优选为1：2～50。
作为本申请粘结剂的一种改进，具有异氰酸酯基团的化合物含有至少 两个异氰酸酯基团。进一步优选含有2～6个异氰酸酯基团。优选的，异氰酸酯基团位于化合物分子结构的两端，即当具有异氰酸酯基团的化合物为一长链化合物时，长链分子的两端均连接有异氰酸酯基团。
作为本申请粘结剂的一种改进，具有异氰酸酯基团的化合物的摩尔质量为100～5000g/mol。
作为本申请粘结剂的一种改进，当第一组分为多异氰酸酯基团化合物时，第一组分与第二组分的质量比为1：1～200，优选为1：2～50。
作为本申请粘结剂的一种改进，第一反应官能团与第二反应官能团的反应温度60～180℃。本申请需要加热后形成粘结，因此更便于控制。
作为本申请粘结剂的一种改进，多环氧基团化合物可选自缩水甘油醚型、缩水甘油酯型或缩水甘油胺型，其中缩水甘油醚型中的官能团为如式II所示，缩水甘油酯型中的官能团为如式III所示，缩水甘油胺型中的官能团为如式IV所示：
Figure PCTCN2016102020-appb-000006
作为本申请粘结剂的一种改进，多环氧基团化合物可选自脂肪族型环氧树脂，具体结构式如式IA～式ID所示：
Figure PCTCN2016102020-appb-000007
其中，R11、R12、R13、R14各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基；取代基选自羟基、羧基、卤素。
其中，R11、R12、R13、R14作为中间连接基团，环氧基团位于中间连接基团的同一个碳原子或不同的碳原子上，优选的，位于不同的碳原子上。
优选的，R11、R12、R13、R14各自独立的分别选自取代或未取代的C6～ 20亚烷基，取代或未取代的C6～20亚烯基。
作为本申请粘结剂的一种改进，多环氧基团化合物可选自缩水甘油醚型环氧化合物，具体结构式如式IIA～式IID所示：
Figure PCTCN2016102020-appb-000008
作为本申请粘结剂的一种改进，多环氧基团化合物可选自缩水甘油酯型环氧化合物，具体结构式如式IIIA～式IIID所示：
Figure PCTCN2016102020-appb-000009
作为本申请粘结剂的一种改进，多环氧基团化合物可选自缩水甘油酯型环氧化合物，具体结构式如式IVA所示：
Figure PCTCN2016102020-appb-000010
在以上通式中，R21、R22、R23、R24、R31、R32、R33、R34、R4各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
优选的，R21、R22、R23、R24、R31、R32、R33、R34、R4各自独立的分别选自取代或未取代的C6～20亚烷基，取代或未取代的C6～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～18亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基。
其中，R21、R22、R23、R24、R31、R32、R33、R34、R4作为中间连接基团，环氧基团位于中间连接基团的同一个碳原子或不同的碳原子上，优选的，位于不同的碳原子上。
作为本申请粘结剂的一种改进，多环氧基团化合物选自双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、季戊四醇缩水甘油醚、1,4-丁二醇缩水甘油醚、丙二醇缩水甘油醚、苯二甲酸缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、六氢邻苯二甲酸二缩水甘油酯、4,4’-二氨基二苯甲烷四缩水甘油基环氧、三缩水甘油基对氨基苯酚、1,3-双(N,N-二缩水甘油氨甲基)环己烷、四缩水甘油-1,3-双(氨甲基环己烷)、9,9-二[(2,3-环氧丙氧基)苯基]芴、1,4-环己烷二甲醇二缩水甘油醚、四缩水甘油基-4,4’-二氨基二苯醚、四缩水甘油基-3,4’-二氨基二苯醚中的至少一种。
除以上具体化合物外，本申请中多环氧基团化合物还可选自：
Figure PCTCN2016102020-appb-000011
本申请中的多官能团环氧化合物，可以通过相应的小分子前躯体，与NaOH、环氧氯丙烷在一定条件下反应得到，其小分子前躯体可选为：双酚A、双酚F、双酚S、季戊四醇、1,4-丁二醇、丙二醇、苯二甲酸、苯二甲酸酐、四氢邻苯二甲酸、四氢邻苯二甲酸酐、六氢邻苯二甲酸、六氢邻苯二甲酸酐、4,4'-二氨基二苯甲烷、对氨基苯酚、1，3-二甲酰胺基环己烷、1,3-二氨甲基环己烷、9,9-双(4-羟苯基)芴9,9-二苯基芴、1,4-环己烷二甲醇。
作为本申请粘结剂的一种改进，当第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物的结构式如下所示：
Figure PCTCN2016102020-appb-000012
其中，R5选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
优选的，R5选自取代或未取代的C6～20亚烷基，取代或未取代的C6～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～18亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
其中，R5作为中间连接基团，环氧基团位于中间连接基团的同一个碳原子或不同的碳原子上，优选的，位于不同的碳原子上。
作为本申请粘结剂的一种改进，第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰 酸酯、1,5-萘二异氰酸酯、二甲基联苯二异氰酸酯、六亚甲基二异氰酸酯、2,2,4-三甲基己二异氰酸酯、2,4,4-三甲基己二异氰酸酯、苯二甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基环己烷二异氰酸酯、1,4苯二异氰酸酯、降冰片烷二异氰酸酯中的至少一种。
在本申请的上述通式中：
碳原子数为1～20的亚烷基，亚烷基可为链状亚烷基，也可为环亚烷基，位于环亚烷基的环上的氢可被烷基取代，所述亚烷基中碳原子数优选的下限值为2，3，4，5，优选的上限值为3，4，5，6，8，10，12，14，16，18。优选地，选择碳原子数为1～18的亚烷基，进一步优选地，选择碳原子数为1～12的链状亚烷基，碳原子数为3～8的环亚烷基，更进一步优选地，选择碳原子数为1～8的链状亚烷基，碳原子数为5～7的环亚烷基。作为亚烷基的实例，具体可以举出：亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基。
碳原子数为2～20的亚烯基可为环状亚烯基，也可为链状亚烯基。另外，亚烯基中双键的个数优选为1个。所述亚烯基中碳原子数优选的下限值为3，4，5，优选的上限值为3，4，5，6，8，10，12，14，16，18。优选地，选择碳原子数为2～18的亚烯基，进一步优选地，选择碳原子数为2～12的亚烯基，更进一步优选地，选择碳原子数为2～8的烯基。作为烯基的实例，具体可以举出：亚乙烯基、亚烯丙基、亚戊烯基、亚环己烯基、亚环庚烯基、亚环辛烯基。
碳原子数为6～26的亚芳基，例如亚苯基、亚苯烷基、至少含有一个亚苯基的芳基如亚联苯基、亚稠环芳烃基如亚萘、亚蒽、亚菲均可，联苯基和稠环芳烃基还可被烷基或是烯基所取代。优选地，选择碳原子数为6～22的亚芳基，进一步优选地，选择碳原子数为6～16的亚芳基，更进一步优选地，选择碳原子数为6～12的亚芳基。作为芳基的实例，具体可以举出：亚苯基、亚苄基、联苯基、对甲亚苯基、邻甲亚苯基、间甲亚苯基。
作为本申请粘结剂的一种改进，第二反应官能团选自羟基、羧基、 -NHR1中至少一种，R1选自H、取代或未取代的烃基，取代基选自卤素。
作为本申请粘结剂的一种改进，具有第二反应官能团的聚合物的选自纤维素醚聚合物、聚丙烯酰胺聚合物、聚乙烯醇聚合物、聚丙烯酸类聚合物中的至少一种。
作为本申请粘结剂的一种改进，具有第二反应官能团的聚合物选自羧甲基纤维素钠、羟乙基纤维素、羧甲基羟乙基纤维素钠、羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素、羟乙基甲基纤维素、乙基纤维素、苄基纤维素、氰乙基纤维素、苄基氰乙基纤维素、苯基纤维素、聚丙烯酰胺、聚甲基丙烯酰胺、聚乙烯醇、海藻酸钠中的至少一种。
作为本申请粘结剂的一种改进，粘合剂中还含有分离的第三组分，所述第三组分选自乳液粘结剂。第一反应官能团可与第三组分进一步发生化学反应，形成三维交联结构，提高极片粘结力和内聚力。
当第一组分为多环氧基团化合物时，第一组分、第二组分与第三组分的质量比为1：1～200：1～200，优选为1：2～50：2～50。
作为本申请粘结剂的一种改进，第一组分、第二组分与第三组分的质量比为1：1～200：1～200，优选为1：2～50：2～50。
作为本申请粘结剂的一种改进，乳液粘结剂可以是苯丙橡胶或其衍生物、丁苯橡胶或其衍生物、纯丙橡胶或其衍生物、丁腈橡胶或其衍生物、氯丁橡胶或其衍生物中的至少一种。
本申请的粘结剂在使用过程时，需将独立的第一组分和第二组分按比例加到水中，获得粘结剂浆料，将该浆料涂覆于需要粘结的部位用于两个部件之间的粘接，也可用于颗粒状物质的粘接。应用该浆料后，将待粘结物体加热至60～180℃，持续时间1～120分钟，从而使环氧基团或异氰酸酯基团与第二反应官能团在加热条件下发生反应形成化学键，完成粘接。
本申请还涉及该粘合剂的应用，具体的，其应用于二次电池领域；进一步优选的，其作为二次电池极片的粘合剂，进一步优选的，其作为二次电池负极极片的粘合剂。
本申请还涉及一种电化学储能装置，含有正极极片、负极极片、电解液和隔离膜，正极极片、负极极片和隔离膜中至少一种含有本申请的粘结 剂。本申请的粘合剂可用于正极极片/负极极片中活性物质层的制备，将正极活性物质/负极活性物质制备成浆料涂覆于集流体上，经干燥得到正极极片/负极极片。或者，本申请的粘合剂也可用于涂覆于隔离膜上，用于将正极极片与隔离膜的粘结，或者用于负极极片与隔离膜的粘结。
本申请的粘结剂特别适用于负极极片的制备，二次电池的水性负极浆料的制备过程中，将石墨添加到水中进行搅拌，并在搅拌过程中，分别添加本申请粘结剂的第一组分和第二组分，利用极片烘干过程中的加热，具有第一反应官能团的第一组分与具有第二反应官能团的第二组分发生化学反应，形成三维网状交联结构。在保证二次电池的电性能的前提下，能明显降低二次电池在制作过程中的负极极片不可逆膨胀，降低电池厚度，提高能量密度，减小循环过程中不可逆膨胀，提高循环寿命。
当第一反应官能团为环氧基团时，第一组分为具有至少两个环氧基团的化合物，而如果第一组分为仅具有一个环氧基团的化合物时，反应后不能产生交联结构，无法满足负极极片制备过程中对粘合剂的要求。
进一步优选的，选用至少含有三个环氧基团的多官能团环氧化合物作为用于负极极片粘合剂的第一组分，交联反应效率更高，对抑制负极极片膨胀、减小循环膨胀的效果更好。
同样，当第一反应官能团为异氰酸酯基团时，在优选的技术方案中，第一组分为具有至少两个异氰酸酯基团的化合物，交联反应效率更高，对抑制负极极片膨胀、减小循环膨胀的效果更好。
进一步优选的，本申请的阴极极片中的第一组分为多环氧基团化合物时，其分子量范围在100～10000(g/mol)，在该范围下，多环氧基团化合物的粘性低，在水中具有较好的分散性，因此可在水性负极浆料中分散均匀。
作为本申请电化学储能装置的一种改进，第一组分在负极极片中的质量百分比含量为0.01％～2％，第二组分在负极极片中的质量百分比含量为0.1～3％。
作为本申请电化学储能装置的一种改进，负极极片中还含有第三组分，第三组分为乳液粘结剂，乳液粘结剂的表面通常都具有水性的-COOH 等基团，第一反应官能团可与第三组分进一步发生化学反应，形成三维交联结构，提高极片粘结力和内聚力。
在本申请电化学储能装置中的负极极片中，第二组分可选自纤维素醚聚合物，纤维素醚聚合物的结构中含有-COOH和-OH，第一反应官能团可同时与-COOH和-OH反应，形成三维交联。从而进一步提高极片内聚力，可以减小负极极片在冷压后的膨胀，降低电池循环过程中的反弹，提高电池能量密度，延长循环寿命。
作为本申请电化学储能装置的一种改进，在本申请的负极极片中，第二组分选自纤维素醚聚合物，并同时添加乳液粘结剂作为第三组分，乳液粘结剂的表面通常都具有水性的-COOH等基团，第一反应官能团同时与第二组分和第三组分进一步发生化学反应，从而进一步提高提高极片粘结力和内聚力。
实施例1
本实施例提供一种粘合剂，其组成如表1所示：
表1：
Figure PCTCN2016102020-appb-000013
Figure PCTCN2016102020-appb-000014
“—”表示未添加该物质。
上述粘合剂在使用时，将分离的第一组分、第二组分和第三组分按比例混合后进行使用。第一组分与第二组分的质量比为1：1～200，优选为1：2～50；第一组分、第二组分与第三组分的质量比为1：1～200：1～200，优选为1：2～50：2～50。
粘合剂粘结力测试：
浸泡电解液前：将各组分材料混合均匀，均匀涂在钢板上，加热烘干，在100℃下烘烤1小时。贴双面胶(宽度10mm)，用2000g压辊在负极片的表面来回滚压三次(300mm/min)。将双面胶180度弯折，手动剥开25mm(粘合剂与钢板剥离)，将该样品固定在试验机上，使剥离面与试验机力线保持一致，试验机以300mm/min连续剥离，得到的剥离力曲线，取平稳段的均值作为剥离力F’，则被测试负极片的粘结力为：F＝F’/0.01＝100F’。
浸泡电解液后：将各组分材料混合均匀，均匀涂在钢板上，加热烘干，在100℃下烘烤1小时，浸泡在电解液(与锂离子电池制备过程中的电解液相同)中，放在干燥环境中(相对湿度<5％)在室温下浸泡24小时，之后取出使其在干燥环境中自然挥发，待负极片表面的有机溶剂挥发完，测试负极片粘结力。测试方法以及粘结力计算方法同上。
检测本实施例中的粘结剂的粘结力如表2所示：
表2：
  浸泡电解液前粘结力(N/m) 浸泡电解液后粘结力(N/m)
1 21.3 3.7
2 24.6 4.1
3 88.3 31.9
4 82.5 29.1
5 91.6 33.5
6 77.7 28.2
7 84.4 32.7
8 88.8 30.6
9 91.7 39.5
10 52.4 18.3
11 82.5 31.7
12 79.8 30.2
13 92.6 38.8
14 81.3 31.0
15 85.9 33.5
16 78.2 28.1
实施例2
本实施例提供一种粘合剂，其组成如表3所示：
表3：
Figure PCTCN2016102020-appb-000015
Figure PCTCN2016102020-appb-000016
“—”表示未添加该物质。
上述粘合剂在使用时，将分离的第一组分、第二组分和第三组分按比例混合后进行使用。
粘合剂粘结力测试方法同实施例1：
检测本实施例中的粘结剂的粘结力如表4所示：
表4：
  浸泡电解液前粘结力(N/m) 浸泡电解液后粘结力(N/m)
1 19.2 4.1
2 21.8 4.5
3 67.0 27.4
4 63.2 25.2
5 69.2 28.6
6 59.9 24.6
7 64.4 28.0
8 67.4 26.4
9 69.3 33.0
10 42.4 16.8
11 63.2 27.2
12 61.3 26.1
13 69.9 32.5
14 62.3 26.7
15 65.4 28.6
16 60.3 24.5
实施例3
本实施例提供使用本申请粘合剂的负极极片及其锂离子电池，锂离子电池包括正极极片、负极极片、隔离膜和电解液，正极极片包括正极集流体和正极活性物质层。
负极片包括负极集流体和负极活性物质层，负极集流体是铜箔，厚度为8μm。按照质量分数，负极极片中活性物质层的组成如表5所示：
表5：
Figure PCTCN2016102020-appb-000017
Figure PCTCN2016102020-appb-000018
其中：“—”表示未添加该物质，负极导电剂选用乙炔黑，丁苯橡胶乳液的型号为日本Zeon，BM400。
按照质量分数，本实施例锂离子电池的正极极片中活性物质层的组成为：
正极活性物质为LiCoO2，含量96.0％；
正极粘结剂为聚偏氟乙烯，分子量60万～120万，含量2.0％；
正极导电剂含量为2.0％；
正极集流体是铝箔，厚度为12μm。
隔离膜为聚乙烯隔离膜，厚度10μm。
电解液包括有机溶剂和锂盐，有机溶剂为碳酸二乙酯，碳酸二甲酯，碳酸乙烯酯的混合物，三种溶剂的体积比例为1：1：1，锂盐为LiPF6，浓度为1mol/L。
锂离子电池的制备：
1、正极极片的制备：将96.0％钴酸锂LiCoO2，2.0％聚偏氟乙烯PVdF，2.0％正极导电剂加入NMP中，搅拌均匀，涂覆在铝箔上，经过干燥、辊压、分切、焊接正极极耳后得到正极片；
2、负极极片的制备：按表5所示的组分，加入蒸馏水中搅拌均匀，涂覆在铜箔上，经过干燥、辊压、分切、焊接负极极耳后得到负极极片；
3、电池的制备：将正极极片、负极极片以及隔离膜卷绕成电芯，将电芯置于铝塑膜中，烘烤除水，再注入电解液，对电芯进行化成和老化，得到相应的锂离子电池B1～B7。
对比例1：
按照实施例3中的方法制备负极极片，区别在于负极极片的组成如表6所示：
表6：
Figure PCTCN2016102020-appb-000019
按照实施例3中的方法制备锂离子电池，得到相应的锂离子电池BD1～BD4。
对比例2：
按照实施例3中的方法制备负极极片，区别在于负极极片的组成如表7所示：
表7：
Figure PCTCN2016102020-appb-000020
其中：壳牌1009环氧树脂的环氧当量约为3000，壳牌1007环氧树 脂的环氧当量约为2000。
按照实施例3中的方法制备锂离子电池，得到相应的锂离子电池BD5～BD8。
实验例：电池性能测试：
1.极片与电池厚度测试
极片厚度：取不同状态的锂电池负极极片，采用千分尺(日本Mitutoyo，型号293)测试极片厚度。每条极片测试点数量不少于10个，取均值作为极片厚度，数据见表8；
Figure PCTCN2016102020-appb-000021
其中：半充时活性物质层厚度＝半充时极片厚度-集流体厚度；
冷压后活性物质层厚度＝冷压后极片厚度-集流体厚度。
电池厚度：采用千分尺测试电池厚度，每个电池测试3组数据，取均值作为电池厚度值，测试数据见表9。
2.电池放电倍率性能测试
1)常温下，以0.5C恒流充电到4.35V，恒压充电至0.05C截止。0.5C恒流放电至3.0V截止，记录容量，以此容量为100％；
2)常温下，以1.0C恒流充电到4.35V，恒压充电至0.05C截止。0.5C恒流放电至3.0V截止，记录容量，计算百分比；
3)常温下，以1.5C恒流充电到4.35V，恒压充电至0.05C截止。0.5C恒流放电至3.0V截止，记录容量，计算百分比；
4常温下，以2.0C恒流充电到4.35V，恒压充电至0.05C截止。0.5C恒流放电至3.0V截止，记录容量，计算百分比。
测试数据见表10。
3.电池循环性能测试
1)常温下，0.5C恒流充电到4.35V，恒压充电至0.05C截止；
2)0.5C恒流放电到3.0V截止，记录容量，以第一次电池容量为100％；
3)重复1-2步骤，以第一次循环时的容量及厚度为100％，记录电池 剩余容量百分比，及电池厚度变化。
测试数据见表11。
表8：极片厚度数据
Figure PCTCN2016102020-appb-000022
表9：电池厚度数据(3.8V)
Figure PCTCN2016102020-appb-000023
Figure PCTCN2016102020-appb-000024
表10：电池放电倍率性能
锂离子电池编号 0.5C 1.0C 1.5C 2.0C
BD1 100.0％ 93.3％ 78.4％ 52.3％
BD2 100.0％ 93.7％ 79.2％ 54.2％
BD3 100.0％ 93.5％ 77.9％ 51.9％
BD4 100.0％ 94.1％ 74.3％ 46.8％
BD5 100.0％ 94.3％ 78.9％ 54.5％
BD6 100.0％ 93.9％ 77.2％ 52.9％
BD7 100.0％ 93.7％ 76.1％ 52.1％
BD8 100.0％ 92.0％ 73.5％ 45.7％
B1 100.0％ 94.5％ 79.8％ 54.2％
B2 100.0％ 94.1％ 79.5％ 54.0％
B3 100.0％ 92.7％ 77.2％ 51.3％
B4 100.0％ 94.4％ 78.5％ 54.1％
B5 100.0％ 94.8％ 78.0％ 52.9％
B6 100.0％ 94.4％ 78.8％ 53.2％
B7 100.0％ 93.3％ 78.4％ 52.3％
B8 100.0％ 95.9％ 82.7％ 60.9％
表11：电池循环剩余容量及厚度
Figure PCTCN2016102020-appb-000025
Figure PCTCN2016102020-appb-000026
如上表数据所示，将本申请中的粘合剂应用于锂离子电池的负极极片中时，电池电性能正常，可明显抑制负极极片冷压后的反弹，并减小电池厚度，提高能量密度。
当对比例中不添加本申请粘合剂中的第一组分时，第二组分仅只能起到增稠和稳定浆料的作用，而第三组分起到粘结作用，无法与负极活性材料完成三维交联，因此无法抑制负极在冷压后及循环过程中的反弹作用，对比例中极片和电池的厚度均发生了显著的增厚，经拆解后发现，负极极片发生了不可逆的膨胀，锂离子电池的电性能也无法得到保障。
当对比例中使用仅含有一个环氧基团的化合物作为第一组分时，无法形成有效的三维交联结构，与不添加时无明显区别，对极片冷压后的极片厚度反弹和循环过程中的膨胀无明显抑制作用。并且即便增加仅含有一个环氧基团的化合物的用量，对冷压后反弹和循环过程中膨胀的也无明显抑制作用，还会降低活性物质所占比例，影响电芯的能量密度。
当对比例中使用了分子量过大或环氧当量过小的化合物作为第一组 分时，由于第一组分的环氧当量小，与其他组分发生交联反应时，反应效率低，形成的三维交联结构有限，对极片冷压后的反弹和循环过程中的膨胀有一定帮助，但是效果不够明显。
当对比例中第一组分添加量过大，没有继续增加极片反弹的趋势，且会影响电池中活性物质的所占比例，影响电芯的能量密度。而第一组分添加量过小，则效果不够明显。
经本申请的实施例的结果证实，本申请粘合剂中的第一组分添加量在0.2％左右时相对效果较好，综合性能具有优势。在电池循环过程中，也可以明显降低电池不可逆循环膨胀，有利于提升电池循环寿命。而当其添加量过低，无法形成稳固的三维交联结构；而当其添加量过大，对厚度的改善无进一步增加的趋势，且还会影响负极极片的能量密度。
采用实施例1和实施例2中的其他粘合剂进行负极极片的制备，获得的锂离子电池的性能与实验例相似，限于篇幅，不再赘述。
本申请虽然以较佳实施例公开如上，但并不是用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (18)

  1. 一种粘结剂，其特征在于，所述粘结剂含有分离的第一组分和第二组分，
    所述第一组分中含有至少一种具有第一反应官能团的化合物，所述第一反应官能团选自环氧基团或异氰酸酯基团中的至少一种；
    所述第二组分中含有至少一种具有第二反应官能团的聚合物；
    所述第一反应官能团具有与所述第二反应官能团反应的活性，且所述第一反应官能团与所述第二反应官能团反应形成化学键；
    当所述第一反应官能团选自环氧基团时，具有环氧基团的化合物中含有至少两个环氧基团。
  2. 根据权利要求1所述的粘结剂，其特征在于，所述具有环氧基团的化合物中含有至少三个环氧基团。
  3. 根据权利要求1所述的粘结剂，其特征在于，所述具有环氧基团的化合物的环氧当量为50～1000。
  4. 根据权利要求1所述的粘结剂，其特征在于，所述具有环氧基团的化合物的摩尔质量为100～10000g/mol。
  5. 根据权利要求1所述的粘结剂，其特征在于，所述具有异氰酸酯基团的化合物含有至少两个异氰酸酯基团。
  6. 根据权利要求1所述的粘结剂，其特征在于，所述具有异氰酸酯基团的化合物的摩尔质量为100～5000g/mol。
  7. 根据权利要求1所述的粘结剂，其特征在于，所述具有环氧基团的化合物选自具有以下基团的化合物：
    Figure PCTCN2016102020-appb-100001
  8. 根据权利要求1所述的粘结剂，其特征在于，所述具有环氧基团 的化合物的结构式如下所示：
    Figure PCTCN2016102020-appb-100002
    Figure PCTCN2016102020-appb-100003
    其中，R11、R12、R13、R14各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基；
    R21、R22、R23、R24、R31、R32、R33、R34、R4各自独立的分别选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
    取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
  9. 根据权利要求1所述的粘结剂，其特征在于，所述带有环氧基团的化合物选自双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚S二缩水甘油醚、季戊四醇缩水甘油醚、1,4-丁二醇缩水甘油醚、丙二醇缩水甘油醚、苯二甲酸缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、六氢邻苯二甲酸二缩水甘油酯、4,4’-二氨基二苯甲烷四缩水甘油基环氧、三缩水甘油基对氨基苯酚、1,3-双(N,N-二缩水甘油氨甲基)环己烷、四缩水甘油-1,3-双(氨甲基环己烷)、9,9-二[(2,3-环氧丙氧基)苯基]芴、1,4-环己烷二甲醇二缩水甘油醚、四缩水甘油基-4,4’-二氨基二苯醚、四缩水甘油基-3,4’-二氨基二苯醚中的至少一种。
  10. 根据权利要求1所述的粘结剂，其特征在于，所述第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物的结构式如下所示：
    Figure PCTCN2016102020-appb-100004
    其中，R5选自取代或未取代的C1～20亚烷基，取代或未取代的C2～20 亚烯基，取代或未取代的C6～26亚芳基，由取代或未取代的C1～20亚烷基、取代或未取代的C6～26亚芳基和酰基中的至少两种连接而成的取代基；
    取代基选自羟基、羧基、卤素、C1～6直链或支链烷基。
  11. 根据权利要求1所述的粘结剂，其特征在于，所述第一反应官能团选自异氰酸酯基团时，具有异氰酸酯基团的化合物选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、二甲基联苯二异氰酸酯、六亚甲基二异氰酸酯、2,2,4-三甲基己二异氰酸酯、2,4,4-三甲基己二异氰酸酯、苯二甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基环己烷二异氰酸酯、1,4苯二异氰酸酯、降冰片烷二异氰酸酯中的至少一种。
  12. 根据权利要求1所述的粘结剂，其特征在于，所述第二反应官能团选自羟基、羧基、-NHR1中至少一种，R1选自H、取代或未取代的烃基，取代基选自卤素。
  13. 根据权利要求1所述的粘结剂，其特征在于，所述具有第二反应官能团的聚合物的选自纤维素醚聚合物、聚丙烯酰胺聚合物、聚乙烯醇聚合物、聚丙烯酸类聚合物中的至少一种。
  14. 根据权利要求13所述的粘结剂，其特征在于，所述具有第二反应官能团的聚合物选自羧甲基纤维素钠、羟乙基纤维素、羧甲基羟乙基纤维素钠、羟丙基纤维素、羟丙基甲基纤维素、甲基纤维素、羟乙基甲基纤维素、乙基纤维素、苄基纤维素、氰乙基纤维素、苄基氰乙基纤维素、苯基纤维素、聚丙烯酰胺、聚甲基丙烯酰胺、聚乙烯醇、海藻酸钠中的至少一种。
  15. 根据权利要求1所述的粘结剂，其特征在于，所述粘合剂中还含有分离的第三组分，所述第三组分选自乳液粘结剂。
  16. 根据权利要求15所述的粘结剂，其特征在于，所述乳液粘结剂可以是苯丙橡胶或其衍生物、丁苯橡胶或其衍生物、纯丙橡胶或其衍生物、丁腈橡胶或其衍生物、氯丁橡胶或其衍生物中的至少一种。
  17. 一种电化学储能装置，含有正极极片、负极极片、电解液和隔离 膜，其特征在于，所述正极极片、负极极片和隔离膜中至少一种含有如权利要求1～16中任一权利要求所述的粘结剂。
  18. 根据权利要求17所述的电化学储能装置，其特征在于，所述第一组分在所述负极极片中的质量百分比含量为0.01％～2％，所述第二组分在所述负极极片中的质量百分比含量为0.1％～3％。
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CN110350195A (zh) * 2019-06-24 2019-10-18 北京科技大学 一种锂离子电池负极粘结剂及锂离子电池负极的制备方法
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CN115336067A (zh) * 2021-10-08 2022-11-11 宁德新能源科技有限公司 电化学装置和电子装置
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