WO2019061675A1 - 结合涂布烘干工艺的锂离子电池交联型水性粘结剂的制备方法 - Google Patents

结合涂布烘干工艺的锂离子电池交联型水性粘结剂的制备方法 Download PDF

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WO2019061675A1
WO2019061675A1 PCT/CN2017/109004 CN2017109004W WO2019061675A1 WO 2019061675 A1 WO2019061675 A1 WO 2019061675A1 CN 2017109004 W CN2017109004 W CN 2017109004W WO 2019061675 A1 WO2019061675 A1 WO 2019061675A1
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lithium ion
ion battery
group
hydroxyl group
current collector
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PCT/CN2017/109004
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English (en)
French (fr)
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张灵志
仲皓想
刘姝伶
苏静
黄进鑫
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中国科学院广州能源研究所
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Priority to US16/490,905 priority Critical patent/US11271209B2/en
Publication of WO2019061675A1 publication Critical patent/WO2019061675A1/zh

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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
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a crosslinked type aqueous binder for a lithium ion battery combined with a coating drying process.
  • the performance of the binder directly affects the electrochemical performance of the battery.
  • the adhesive should have sufficient elasticity to relieve the expansion and contraction of the battery during charging and discharging, and loosen and fall off, which facilitates the conduction of electrons and ions during charging and discharging, and reduces the current collector.
  • the impedance between the electrode material and the electrode material In the large-scale production of the lithium ion battery industry, polyvinylidene fluoride (PVDF) is used as a binder, and an organic solvent N-methylpyrrolidone (NMP) is used as a dispersing agent.
  • PVDF polyvinylidene fluoride
  • NMP organic solvent N-methylpyrrolidone
  • Aqueous binders such as styrene-butadiene rubber (SBR)/sodium carboxymethyl cellulose (CMC) and polyacrylic acid have been used in large-scale markets, but their adhesion but their adhesion, flatness and inhibition of pole pieces The effect of pole piece expansion is limited, so its scope of use is limited.
  • SBR styrene-butadiene rubber
  • CMC sodium carboxymethyl cellulose
  • polyacrylic acid have been used in large-scale markets, but their adhesion but their adhesion, flatness and inhibition of pole pieces The effect of pole piece expansion is limited, so its scope of use is limited.
  • Multi-functionalized modified polymer lithium ion battery binder (CN 2016105083512), using biomass polymer or synthetic polymer as substrate, hydrophilic monomer and lipophilic monomer as functional modification monomer,
  • the aqueous binder prepared by radical graft copolymerization or Michael addition reaction can improve the uniformity and flatness of the electrode paste film formation, and the modified polyvinyl alcohol polymer (CN 2016105041083), through Michael Plus
  • the invention discloses the introduction of acrylic acid and its salts with good water solubility, acrylonitriles with good bonding properties and electrochemical properties, or acrylamide monomers with good flexibility into PVA molecules, and prepared water-soluble water-soluble adhesives with good water solubility. Conjunction. However, there is still a deficiency in suppressing the expansion of the pole piece, especially the high theoretical capacity Si negative electrode having a serious volume effect.
  • the polymer having a crosslinked structure has high molecular cohesion, better adhesion and elasticity, and can effectively suppress the expansion of the pole piece. Therefore, research and development of lithium ion battery cross-linking type water-based adhesive to improve electrode adhesion and elasticity, further improve battery performance and reduce production cost is currently a hot spot.
  • CN 104356979B discloses a polyacrylate-based aqueous binder for a lithium ion battery electrode material and a preparation method thereof, which are obtained by polymerization and crosslinking of an unsaturated monomer, and then the crosslinked polymer binder is further
  • the utility model relates to a lithium ion battery, wherein the adhesive has insufficient adhesion, dispersibility and elasticity, and the degree of crosslinking of the adhesive needs to be controlled, otherwise the bonding effect cannot be achieved, and the synthetic process has certain difficulty. There is currently no big Scale use.
  • An object of the present invention is to provide a method for preparing a crosslinked type aqueous binder for a lithium ion battery, which comprises crosslinking an aqueous polymer containing an organic carboxylic acid or an amino group or a hydroxyl group with a water-soluble small molecule containing a hydroxyl group, an amine group or a carboxyl group.
  • the agent is cross-linked by esterification and amidation reaction under the coating and drying conditions of the lithium ion battery electrode sheet, and the preparation process is simple, no additional processing conditions are required, and good bonding is obtained.
  • the electrode with flexibility, flexibility and elasticity solves the problem that the bonding strength between the electrode active material, the conductive agent and the current collector in the prior art is not high, and does not have sufficient elasticity to alleviate the expansion during charging and discharging of the lithium ion battery.
  • a method for preparing a cross-linked aqueous binder for a lithium ion battery which comprises an aqueous polymer containing an organic carboxylic acid or an amino group or a hydroxyl group and a water-soluble small molecule crosslinking agent having a hydroxyl group, an amine group or a carboxyl group as an aqueous binder
  • the raw material is crosslinked by esterification and amidation reaction under the coating and drying conditions of the lithium ion battery electrode sheet slurry, and the molecular weight of the aqueous polymer containing organic carboxylic acid or amino group or hydroxyl group is 70,000 to 1,000,000, and the solid content is
  • the aqueous polymer containing the organic carboxylic acid group is modified by a free radical graft copolymerization reaction or a Michael addition reaction by using an acrylic acid monomer and a hydroxyl group-containing aqueous polymer in an amount of 1 to 50% and a viscosity of 1 to 50,000 mPa ⁇
  • the hydroxyl-containing aqueous polymer is selected from the group consisting of gum arabic, cyclodextrin, cellulose derivatives, xanthan gum, pectin, gelatin, starch, phthalocyanine, polyvinyl alcohol, polyethylene glycol, and more One or more of hydroxypolybutadiene;
  • the amino group-containing aqueous polymer is selected from the group consisting of gum arabic, chitosan and derivatives thereof, linear polyethyleneimine, and branched polyethyleneimine. Or two or more; the method Comprising the steps of:
  • step 2) adding a water-soluble small molecule crosslinking agent containing a hydroxyl group, an amine group or a carboxyl group to the solution obtained in the step 1), and sufficiently stirring to obtain a uniform mixed solution; water-soluble small molecule cross-linking containing a hydroxyl group, an amine group or a carboxyl group;
  • the molar ratio of the agent to the organic polymer containing an organic carboxylic acid or an amino group or a hydroxyl group is 0.01:10 to 1:10;
  • the mixed solution prepared in the step 2) is subjected to a crosslinking reaction at 90 to 130 ° C to obtain a target binder.
  • the aqueous polymer containing an organic carboxylic acid group is obtained by radical graft copolymerization or Michael addition reaction modification of an acrylic monomer and a hydroxyl group-containing aqueous polymer, and the radical graft copolymerization reaction refers to a hydroxyl group-containing water.
  • the polymer and the acrylic monomer are initiated by a radical polymerization or a copolymerization reaction by an initiator;
  • the initiator is selected from the group consisting of (NH 4 ) 2 S 2 O 8 , Na 2 S 2 O 8 , K 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 /NaHSO 3 , (NH 4 ) 2 S 2 O 8 /Na 2 SO 3 , Na 2 S 2 O 8 /NaHSO 3 , Na 2 S 2 O 8 /Na 2 SO 3 ,
  • the initiator is used in an amount of from 0.01 to 5% by weight based on the total mass of the monomers.
  • the Michael addition reaction refers to a Michael addition reaction of a hydroxyl group-containing aqueous polymer and an acrylic monomer through a basic catalyst;
  • the basic catalyst is selected from one of LiOH, NaOH, LiOH/urea, NaOH/urea. kind or more than two.
  • the basic catalyst is used in an amount of from 0.01 to 5% by weight based on the total mass of the monomers.
  • the hydroxyl group-containing water-soluble small molecule crosslinking agent has at least one of the following structural monomers: a saturated diol having 2 or more carbon atoms, a saturated polyol having 3 or more carbon atoms, and a saturated diol amine NH-(C m H 2m -OH) 2 , saturated polyol amine N-(C m' H 2m' -OH) 3 , wherein m ⁇ 1, m' ⁇ 1.
  • the amine-containing water-soluble small molecule crosslinking agent has at least one of the following structural monomers: a saturated diamine CnH 2n (NH 2 ) 2 , a saturated polyamine saturated polyamine C n' H 2n'+2- x (NH 2 ) x , where n ⁇ 2, n' ⁇ 3, and x ⁇ 3.
  • the carboxyl group-containing water-soluble small molecule crosslinking agent has at least one of the following structural monomers: a saturated dibasic acid, and a saturated polybasic acid having 3 or more carbon atoms.
  • the protective atmosphere of step 1) is nitrogen and/or argon, and the stirring speed is 200 to 450 rpm.
  • the water-soluble small molecule crosslinking agent containing a hydroxyl group, an amine group or a carboxyl group is preferably selected from the group consisting of ethylene glycol, pentaerythritol, ethylene glycol amine, triethanolamine, hexamethoxymethyl melamine, adipic acid, etc.
  • the water-soluble small molecule crosslinking agent containing a hydroxyl group, an amine group or a carboxyl group and the aqueous polymer containing an organic carboxylic acid or an amino group or a hydroxyl group are in a molar ratio of 0.5:10 to 1:10.
  • the mixed solution prepared in step 2) is used to prepare a slurry of lithium ion positive and negative materials, and after the slurry is coated with the current collector, the crosslinking agent is cross-linked during the drying process to obtain a target viscosity.
  • the baking agent has a drying temperature of 90-110 ° C.
  • the invention also protects the use of the lithium ion battery cross-linking type aqueous binder in an electrochemical energy storage device, which comprises a lithium ion battery, a secondary battery, a super capacitor, a solar battery.
  • the lithium ion battery cross-linking type aqueous binder is used in a positive electrode sheet of a lithium ion battery;
  • the lithium ion battery positive electrode sheet includes a current collector and a lithium ion battery positive electrode slurry supported on the current collector;
  • the positive electrode slurry of the lithium ion battery includes a positive electrode active material, a conductive agent, and a mixed solution prepared in the second step of the method for preparing a lithium ion battery crosslinked type aqueous binder, and the solid content of the positive electrode slurry of the lithium ion battery 30 to 75%, the viscosity of the lithium ion battery positive electrode slurry is 3000-8000 mPa ⁇ s, and the lithium ion battery positive electrode slurry is coated with a current collector and dried to obtain a target electrode;
  • the positive electrode active material is selected from lithium iron phosphate and cobalt.
  • One or more of lithium acid, lithium manganate or a ternary material LiNi 1/3 Mn 1/3 Co 1/3 O 2 , NMC
  • the conductive agent is acetylene black
  • the current collector is aluminum foil
  • the mass ratio of the solute of the mixed solution prepared in the step 2) in the method for producing the positive electrode active material, the conductive agent and the above-mentioned lithium ion battery crosslinked type aqueous binder is 70 to 95:2 to 20:3 to 10.
  • the lithium ion battery cross-linking type aqueous binder is used in a negative electrode sheet of a lithium ion battery;
  • the lithium ion battery negative electrode sheet includes a current collector and a lithium ion battery negative electrode slurry supported on the current collector;
  • the lithium The negative electrode slurry of the ion battery includes a negative electrode active material, a conductive agent, and a mixed solution prepared in the second step of the method for preparing a lithium ion battery crosslinked type aqueous binder, wherein the lithium ion battery negative electrode slurry has a solid content of 30 ⁇ 75%, the viscosity of the lithium ion battery negative electrode slurry is 3000-8000 mPa ⁇ s, and the lithium ion battery negative electrode slurry is coated with a current collector and dried to obtain a target electrode; the negative electrode active material is selected from a silicon-based material and a lithium titanate.
  • the conductive agent is acetylene black
  • the current collector is copper foil
  • the anode active material, the conductive agent and the above-mentioned lithium ion battery cross-linking type aqueous binder are prepared in the step 2)
  • the mass ratio of the solute of the mixed solution is 70 to 95:2 to 20:3 to 10.
  • the invention also protects a lithium ion battery comprising a battery case, a pole core and an electrolyte, the pole core and the electrolyte being sealed in the battery case, the pole core comprising the electrode piece described above And a diaphragm between the electrode pads.
  • the cross-linked aqueous binder provided by the invention can be applied in an aqueous solvent, and the slurry is cross-linked by a lithium ion battery pole piece drying process to obtain good elasticity, cohesiveness and flexibility.
  • the electrode sheet provides more active sites in contact with the electrode active material, greatly increasing the ion transport rate in the electrolyte, facilitating the conduction of electrons/ions during charge and discharge, and reducing the electrochemical interface impedance.
  • the cross-linking type water-based binder provided by the invention is applied to the positive and negative electrodes of the lithium ion battery, can improve the uniformity and flatness of the electrode paste film formation, and enhance the active material and the conductive agent pair after drying and crosslinking.
  • the peeling strength of the metal substrate greatly enhances the bonding strength between the electrode active material, the conductive agent and the current collector, and greatly improves the cycle stability performance of the positive and negative materials of the lithium ion battery.
  • the preparation method of the crosslinked aqueous binder provided by the invention is simple, environmentally friendly, and has a wide source of synthetic raw materials, abundant resources and low cost, and can be crosslinked by a lithium ion battery pole piece drying process without additional processing.
  • Process conditions, and obtain an electrode with good adhesion, flexibility, elasticity, to solve the bonding strength between the electrode active material, the conductive agent and the current collector in the prior art is not high, and does not have sufficient elasticity to relieve lithium
  • the problem of expansion and contraction of the ion battery during expansion and contraction and loosening and falling off has a broad market prospect and promotes the technological progress of the lithium ion battery industry.
  • the cross-linking type water-based binder provided by the invention overcomes the adhesiveness, dispersibility and elasticity of the binder obtained in the patent CN 104356979B, and needs to control the degree of crosslinking of the binder, otherwise it cannot
  • the disadvantage of bonding, and the crosslinking reaction during the drying process of the pole piece can obtain a binder which is more uniform in dispersion, stronger in binding force, and provides more active sites in contact with the electrode active material.
  • 1-3 are infrared spectra of the crosslinking of the GA-PAA of the present invention with hydroxyl groups, amine groups and the like.
  • Figure 4 is a DSC experiment in which Examples 7-9 of the present invention are GA-PAA and a hydroxyl group, an amine group or the like.
  • Figure 5 is a DSC experiment of the crosslinking of a PVA-PAA-MA of Example 14 of the present invention with a hydroxyl group-containing amine group.
  • Fig. 6 is a graph showing the cycle performance test of a negative electrode material for a negative electrode material obtained by crosslinking a GA-PAA with a hydroxyl group-containing amine group in Example 16 of the present invention.
  • Fig. 7 is a graph showing electrochemical impedance contrast of a silicon negative electrode and a comparative electrode in Example 16 of the present invention.
  • Example 8 is a cross-linking of GA-PAA with a hydroxyl group-containing amine group to obtain a binder for LFP cathode material cycle performance test according to Example 17 of the present invention.
  • Figure 9 is a graph showing electrochemical impedance contrast of lithium iron phosphate and a comparative electrode according to Example 17 of the present invention.
  • GA gum arabic
  • PVA polyethylene glycol
  • PER pentaerythritol
  • PER triethanolamine
  • TEOA hexamethoxymethyl melamine
  • MA methyl acrylate
  • the gum arabic is classified as GA; the aqueous polymer containing organic carboxylic acid group prepared by radical graft copolymerization or Michael addition reaction of acrylic acid monomer and gum arabic is recorded as GA-PAA, and polyethylene glycol is recorded as PVA.
  • the organic polymer containing carboxylic acid group prepared by radical graft copolymerization or Michael addition reaction of acrylic monomer and polyethylene glycol is recorded as PVA-PAA, methyl acrylate, acrylic monomer and polyethylene
  • PVA-PAA-MA The aqueous polymer containing organic carboxylic acid group prepared by radical graft copolymerization or Michael addition reaction is classified as PVA-PAA-MA, pentaerythritol is PER, triethanolamine is TEOA, hexamethoxymethyl Melamine is referred to as HMMM and methyl acrylate is referred to as MA.
  • PVA-PAA the specific preparation method is as follows: PVA is weighed into a two-necked flask, DI-water is added, stirred under an argon atmosphere to completely dissolve, and the temperature is raised to 65 ° C, and Na 2 S 2 O 8 and NaHSO 3 are sequentially added. The aqueous solution and the acrylic monomer are reacted at 65 ° C for 24 hours under an argon atmosphere to obtain a PVA-PAA aqueous polymer; the initiator is used in an amount of 0.01 to 5% by weight based on the total mass of the monomers.
  • step (2) an amine-based small molecule cross-linking agent such as triethanolamine is added to the solution obtained in the step (1), and the amidation reaction is carried out at different temperatures to observe the dissolution.
  • an amine-based small molecule cross-linking agent such as triethanolamine
  • step (2) a hexamethoxymethyl melamine (HMMM) crosslinking agent was added to the solution obtained in the step (1), and esterified at different temperatures. Observe its dissolution.
  • HMMM hexamethoxymethyl melamine
  • GA-PAA can be completely dissolved at 45-90 ° C, and when it is heated to above 110 ° C, cross-linking occurs and swelling occurs.
  • PER pentaerythritol
  • TEOA triethanolamine
  • HMMM hexamethoxymethyl melamine
  • step (2) an amine group-containing small molecule such as triethanolamine is added to the solution obtained in the step (1). See Figure 2 for infrared spectroscopy.
  • step (2) a hexamethoxymethyl melamine (HMMM) crosslinking agent is added to the step (1) and treated at different temperatures. See Figure 3 for its infrared test.
  • HMMM hexamethoxymethyl melamine
  • the crosslinking reaction occurs between GA-PAA and pentaerythritol (PER), triethanolamine (TEOA) or hexamethoxymethyl melamine when heated above 110 °C.
  • PER pentaerythritol
  • TEOA triethanolamine
  • hexamethoxymethyl melamine when heated above 110 °C.
  • Step (2) an amine group-containing small molecule such as triethanolamine was added to the solution obtained in the step (1) to carry out an amidation reaction.
  • Figure 4 is a DSC experiment of crosslinking of GA-PAA with an amine group.
  • GA-PAA reacts with pentaerythritol (PER), triethanolamine (TEOA) or hexamethoxymethyl melamine to cause a cross-linking endothermic reaction when heated above 90 °C.
  • PER pentaerythritol
  • TEOA triethanolamine
  • hexamethoxymethyl melamine hexamethoxymethyl melamine
  • PEI polyethyleneimine
  • DI-Water deionized water
  • step (2) one or more of malonic acid, triglyceride, and adipic acid are added to the solution obtained in the step (1), and the mixture is thoroughly stirred to obtain a mixed solution; the reaction is carried out at a vacuum temperature of 45 ° C and 90 ° C for 1 to 24 hours. Then dissolved in a certain amount of water and observed the dissolution. It can be seen that after heating at 90°, PEI reacts with the above different crosslinking agents.
  • step 1) the polyethyleneimine is replaced with a hydroxyl-containing aqueous polymer polyvinyl alcohol (PVA), and the step (2) is carried out at a vacuum temperature of 45 ° C and 110 ° C for 1 to 24 hours. Observe the solubility test. It can be seen that after heating at 110 ° C, PVA reacts with the above different crosslinking agents.
  • the obtained mixed binder was coated on an Al foil, coated to a thickness of 100 ⁇ m, dried at 110 ° C, and then tested for peel strength, and the peel strength value was measured to be 0.10 N/mm.
  • step 1) GA-PAA is replaced by PVA-PAA
  • step (2) cross-linking agent is pentaerythritol (PER), triethanolamine (TEOA), hexamethoxymethyl melamine (HMMM). , observe its solubility test.
  • PER pentaerythritol
  • TEOA triethanolamine
  • HMMM hexamethoxymethyl melamine
  • Step 1) PVA-PAA was replaced with PVA-PAA-MA, and the solubility test of the crosslinking agent reaction was observed.
  • the lithium ion battery negative electrode sheet includes a current collector and a lithium ion battery negative electrode slurry supported on the current collector; the lithium ion battery negative electrode slurry includes a negative electrode active material, a conductive agent, a binder; and the negative electrode activity
  • the mass ratio of the material, the conductive agent and the binder is 70:20:10, and the solvent is water.
  • the negative active material is silicon; the conductive agent is acetylene black;
  • the current collector is a copper foil current collector; the lithium ion battery negative electrode slurry has a solid content of 30%, and the lithium ion battery negative electrode slurry has a viscosity of 3000 mPa ⁇ s.
  • the peel strength of the prepared GA-PAA-Si-negative electrode is shown in Table 1. It can be seen from the table that the silicon electrode has a high peel strength after cross-linking with different cross-linking agents, wherein the peel strength of GA-PAA-HMMM-Si is up to 0.28 N/mm.
  • Electrode sheet Peel strength (N/mm) GA-PAA-Si 0.18 GA-PAA-PER-Si 0.2 GA-PAA-HMMM-Si 0.28 GA-PAA-TEOA-Si 0.19
  • the lithium ion battery negative electrode sheet comprises a current collector and a lithium ion battery negative electrode slurry supported on the current collector;
  • the lithium ion battery negative electrode slurry comprises a negative electrode active material, a conductive agent, a binder; and a mass ratio of the negative electrode active material, the conductive agent, and the binder of 70:20:10, wherein the solvent is water.
  • the negative active material is silicon; the conductive agent is acetylene black; the current collector is a copper foil current collector; the lithium ion battery negative electrode slurry has a solid content of 75%, and the lithium ion battery negative electrode slurry has a viscosity of 8000mPa ⁇ s.
  • GA-PAA is used as an aqueous binder raw material, dissolved in deionized water, and stirred under a protective atmosphere of argon for 0.5 to 2.5 hours to drive off oxygen to obtain a uniform and dispersible solution; then pentaerythritol (PER), three Ethanolamine (TEOA), hexamethoxymethyl melamine (HMMM) cross-linking agent is added, stirred evenly, the molar ratio of GA-PAA to water-soluble small molecule cross-linking agent is 10:1, silicon and conductive agent Mixing and stirring until uniformly dispersed into the above system, adding appropriate amount of deionized water to adjust viscosity, for preparing lithium ion silicon negative electrode material slurry, obtaining silicon electrode slurry; uniformly preparing the obtained slurry on Cu foil, 110 The vacuum is dried at ° C, and a cross-linking reaction occurs to obtain a silicon negative electrode sheet.
  • PER pentaerythritol
  • TEOA three
  • Electrochemical performance test and electrochemical impedance test of constant current charge and discharge on the test electrode are Electrochemical performance test and electrochemical impedance test of constant current charge and discharge on the test electrode.
  • Fig. 6 is a graph showing the cycle performance test of the silicon electrode at a magnification of 400 mA/g in the present embodiment. It can be seen from the figure that GA-PAA-TEOA-Si and GA-PAA-HMMM-Si anodes prepared by three-dimensional cross-linking modified polymer binder have excellent cycle performance after 60 charge and discharge cycles. After that, its charge specific capacity is higher than 1000 mAh/g, which is far superior to GA-PAA-Si under the same conditions, showing excellent cycle performance and electrochemical stability. It can be seen that the addition of the crosslinking agent can greatly improve the cycle stability of the silicon electrode.
  • Figure 7 shows the electrochemical impedance contrast curves of the silicon negative electrode and the comparative electrode. It can be seen from the figure that the electrochemical impedance of the GA-PAA-TEOA-Si and GA-PAA-HMMM-Si anodes prepared by three-dimensional cross-linking modified polymer binder is less than the same after 60 cycles of charge and discharge. GA-PAA-Si under the conditions. It can be seen that the addition of TEOA and HMMM crosslinkers can reduce the electrochemical impedance of the silicon electrode.
  • the positive electrode sheet of the lithium ion battery includes a current collector and a lithium ion battery positive electrode slurry supported on the current collector;
  • the lithium ion battery positive electrode slurry includes a positive electrode active material, a conductive agent, a binder; and the positive electrode active agent
  • the mass ratio of the material, the conductive agent and the binder is 95:2:3, and the solvent is water.
  • the positive active material is an LFP material;
  • the conductive agent is acetylene black;
  • the current collector is an aluminum foil current collector;
  • the solid content of the lithium ion battery positive electrode slurry is 50%, and the viscosity of the lithium ion battery positive electrode slurry is 5000mPa ⁇ s.
  • GA-PAA is used as an aqueous binder raw material, dissolved in deionized water, and stirred under a protective atmosphere of argon for 0.5 to 2.5 hours to drive off oxygen to obtain a uniform and dispersible solution; Further, a crosslinking agent of pentaerythritol (PER), triethanolamine (TEOA), and hexamethoxymethylmelamine (HMMM) is added, and the molar ratio of GA-PAA to the water-soluble small molecule crosslinking agent is 10:0.1.
  • PER pentaerythritol
  • TEOA triethanolamine
  • HMMM hexamethoxymethylmelamine
  • a comparative electrode was prepared in the same manner using GA-PAA as a binder.
  • Electrochemical testing and electrochemical impedance testing were performed on the charge and discharge cycle stability of the test electrode and the comparative electrode.
  • FIG. 8 is a test performance curve of the LFP electrode and the comparative electrode tested at a charging current density of 0.5 C in the present embodiment.
  • LFP electrodes prepared by three-dimensional cross-linking modified GA-PAA-based polymer lithium ion battery binder have good cycle stability.
  • the GA-PAA-PER-LFP electrode has a higher specific capacity.
  • GA-PAA-LFP, GA-PAA-PER-LFP, GA-PAA The specific capacities of the -HMMM-LFP, GA-PAA-TEOA-LFP electrodes were 135.6, 142.9, 127 and 132 mAh/g, respectively. It can be seen that the addition of the cross-linking agent PER can increase the specific capacity and cycle stability of the LFP electrode.
  • Figure 9 shows the electrochemical impedance contrast curves of the LFP electrode and the comparative electrode. It can be seen from the figure that the GA-PAA-PER-LFP electrode exhibits a lower electrochemical impedance after 50 charge and discharge cycles than the GA-PAA-LFP electrode. The addition of cross-linking PER can improve the electrochemical performance of the LFP electrode.

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Abstract

一种锂离子电池交联型水性粘结剂的制备方法，由含有机羧酸或氨基或羟基的水性高分子与含有羟基、胺基或羧基的水溶性小分子交联剂共同作为水性粘结剂原材料，在锂离子电池电极片浆料涂布烘干条件下经酯化、酰胺化反应交联，制备过程简单，不改变现有的锂离子电池生产工艺条件，且获得具有良好粘结性、柔顺性、弹性的电极，解决现有技术中电极活性物质、导电剂和集流体之间的粘结强度不高，且不具有足够的弹性来缓解锂离子电池充、放电过程中的膨胀与收缩而松胀脱落的问题。

Description

[根据细则37.2由ISA制定的发明名称]　结合涂布烘干工艺的锂离子电池交联型水性粘结剂的制备方法 技术领域：
本发明涉及锂离子电池技术领域，具体涉及一种结合涂布烘干工艺的锂离子电池交联型水性粘结剂的制备方法。
背景技术：
粘结剂作为锂离子电池的重要非活性成分，其性能的优劣直接影响电池的电化学性能。除具有粘结作用外，粘结剂还应具有足够的弹性能缓解电池在充、放电过程中的膨胀与收缩而松胀脱落，利于电子、离子在充放电过程中的传导，减小集流体与电极材料之间的阻抗。在锂离子电池工业的规模化生产中，主要采用聚偏氟乙烯(PVDF)作粘结剂、有机溶剂N-甲基吡咯烷酮(NMP)等作分散剂。但由于PVDF存在电子和离子导电性差，对环境的湿度要求比较高，能耗大，生产成本高，且不具有足够的弹性。因此，寻找替代PVDF的新型绿色粘结剂成为锂离子电池粘结剂的重要发展方向。
水性粘结剂是锂离子电池粘结剂发展的一个重要方向。丁苯橡胶(SBR)/羧甲基纤维素钠(CMC)、聚丙烯酸类等水性粘结剂已经有大规模市场应用，但其粘结力但其粘结力、极片的平整性和抑制极片膨胀的效果均有限，故其使用范围受到一定的限制。一种多元功能化改性高分子锂离子电池粘结剂(CN 2016105083512)，以生物质高分子或合成高分子为底物，以亲水单体和亲油单体作为功能化改性单体，经自由基接枝共聚反应或迈克尔加成反应改性制备的水性粘接剂能提高电极浆料成膜时的均匀性和平整性，改性聚乙烯醇高分子(CN 2016105041083)，通过迈克尔加成引入具有良好水溶性的丙烯酸及其盐类、良好粘结性能和电化学性能的丙烯腈类、或良好柔顺性的丙烯酰胺单体至PVA分子中，制备的具有良好的水溶性的水性粘结剂。但是在针对抑制极片的膨胀，尤其是对体积效应严重的高理论容量的Si负极来说仍有不足。
具有交联结构的聚合物，其分子内聚力大，粘结力和弹性更好，同时能有效抑制极片的膨胀。因此，研究开发锂离子电池交联型水性粘结剂来提高电极粘结性和弹性，进一步改善电池性能，降低生产成本是当前的热点。CN 104356979B公开了一种锂离子电池电极材料的聚丙烯酸酯类水性粘结剂及其制备方法，该材料由不饱和单体聚合同时交联获得，然后将交联后的高分子粘结剂再用于锂离子电池，该粘结剂的粘结力、分散性、弹性不足，且需要控制该粘结剂的交联度，否则不能起到粘接的作用，合成工艺上有一定的难度，目前尚无大 规模使用。
发明内容：
本发明的目的是提供一种锂离子电池交联型水性粘结剂的制备方法，由含有机羧酸或氨基或羟基的水性高分子与含有羟基、胺基或羧基的水溶性小分子交联剂共同作为水性粘结剂原材料，在锂离子电池电极片浆料涂布烘干条件下经酯化、酰胺化反应交联，制备过程简单，无须另外的加工工艺条件，且获得具有良好粘结性、柔顺性、弹性的电极，解决现有技术中电极活性物质、导电剂和集流体之间的粘结强度不高，且不具有足够的弹性来缓解锂离子电池充、放电过程中的膨胀与收缩而松胀脱落的问题。
本发明是通过以下技术方案予以实现的：
一种锂离子电池交联型水性粘结剂的制备方法，由含有机羧酸或氨基或羟基的水性高分子与含有羟基、胺基或羧基的水溶性小分子交联剂共同作为水性粘结剂原材料，在锂离子电池电极片浆料涂布烘干条件下经酯化、酰胺化反应交联，所述含有机羧酸或氨基或羟基的水性高分子的分子量为70000～1000000，固含量为1～50％，粘度为1～50000mPa·s，所述含有机羧酸基的水性高分子由丙烯酸单体与含羟基的水性高分子经自由基接枝共聚反应或迈克尔加成反应改性制备获得，其中，含羟基的水性高分子选自阿拉伯胶、环糊精、纤维素衍生物、黄原胶、果胶、明胶、淀粉、田菁胶、聚乙烯醇、聚乙二醇、多羟基聚丁二烯中的一种或两种以上；所述含氨基水性高分子选自阿拉伯胶、壳聚糖及其衍生物、线性聚乙烯亚胺、支链聚乙烯亚胺中的一种或两种以上；该方法包括以下步骤：
1)将含有机羧酸或氨基或羟基的水性高分子溶解于去离子水中，并在保护性气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；搅拌速度为100～500转/分；
2)将含有羟基、胺基或羧基的水溶性小分子交联剂加到步骤1)得到的溶液中，充分搅拌得到均匀的混合溶液；含有羟基、胺基或羧基的水溶性小分子交联剂与含有机羧酸或氨基或羟基的水性高分子摩尔比为0.01:10～1:10；
3)将步骤2)制备的混合溶液90-130℃进行交联反应得到目标粘结剂。
所述含有机羧酸基的水性高分子由丙烯酸单体与含羟基的水性高分子经自由基接枝共聚反应或迈克尔加成反应改性制备获得，自由基接枝共聚反应指含羟基的水性高分子与丙烯酸单体通过引发剂引发发生自由基聚合或共聚接枝反应；所述引发剂选自(NH4)2S2O8、Na2S2O8、K2S2O8、(NH4)2S2O8/NaHSO3、(NH4)2S2O8/Na2SO3、Na2S2O8/NaHSO3、Na2S2O8/Na2SO3、K2S2O8/NaHSO3、K2S2O8/Na2SO3、Ce(NH4)2(NO3)6、偶氮二异丁基脒盐酸 盐中的一种；所述引发剂的用量为单体总质量的0.01～5wt％。所述迈克尔加成反应指含羟基的水性高分子高分子与丙烯酸单体通过碱性催化剂发生迈克尔加成反应；所述碱性催化剂选自LiOH、NaOH、LiOH/尿素、NaOH/尿素中的一种或两种以上。所述碱性催化剂的用量为单体总质量的0.01～5wt％。
所述含羟基水溶性小分子交联剂具有如下结构单体中的至少一种：碳原子数大于等于2的饱和二元醇、碳原子数大于等于3的饱和多元醇、饱和二元醇胺NH-(CmH2m-OH)2、饱和多元醇胺N-(Cm’H2m’-OH)3，其中m≥1，m’≥1。
所述含胺基水溶性小分子交联剂具有如下结构单体中的至少一种：饱和二元胺CnH2n(NH2)2、饱和多元胺饱和多元胺Cn’H2n’+2-x(NH2)x，其中n≥2，n’≥3，x≥3。
所述含羧基水溶性小分子交联剂具有如下结构单体中的至少一种：饱和二元酸、碳原子数大于等于3的饱和多元酸。
优选地，步骤1)所述保护性气氛为氮气和/或氩气，所述搅拌速度为200～450转/分。
优选地，步骤2)，所述含有羟基、胺基或羧基的水溶性小分子交联剂优选自乙二醇、季戊四醇、乙二醇胺、三乙醇胺、六甲氧甲基三聚氰胺、己二酸等的一种或两种以上；含有羟基、胺基或羧基的水溶性小分子交联剂与含有机羧酸或氨基或羟基的水性高分子摩尔比为0.5:10-1:10。
优选地，步骤3)中将步骤2)制备的混合溶液用于制备锂离子正、负极材料浆料，其浆料涂覆集流体后在烘干过程中交联剂进行交联反应得到目标粘结剂，烘干温度为90-110℃。
本发明还保护所述锂离子电池交联型水性粘结剂在电化学储能器件中的应用，所述电化学储能器件包括锂离子电池、二次电池、超级电容器、太阳能电池。
特别地，所述锂离子电池交联型水性粘结剂应用在锂离子电池的正极片中；所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂和上述锂离子电池交联型水性粘结剂的制备方法中步骤2)制备的混合溶液，所述锂离子电池正极浆料的固体含量为30～75％，锂离子电池正极浆料的粘度为3000～8000mPa·s，锂离子电池正极浆料涂覆集流体后烘干得到目标电极；所述正极活性材料选自磷酸铁锂、钴酸锂、锰酸锂或三元材料(LiNi1/3Mn1/3Co1/3O2，NMC)的一种或多种；所述导电剂为乙炔黑；所述集流体为铝箔；正极活性材料、导电剂和上述锂离子电池交联型水性粘结剂的制备方法中步骤2)制备的混合溶液的溶质的质量比为70～95:2～20:3～10。
所述锂离子电池交联型水性粘结剂应用在锂离子电池的负极片中；所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、和上述锂离子电池交联型水性粘结剂的制备方法中步骤2)制备的混合溶液，所述锂离子电池负极浆料的固体含量为30～75％，锂离子电池负极浆料的粘度为3000～8000mPa·s，锂离子电池负极浆料涂覆集流体后烘干得到目标电极；所述负极活性材料选自硅基材料、钛酸锂或石墨的一种或两种以上；所述导电剂为乙炔黑；集流体为铜箔；负极活性材料、导电剂和上述锂离子电池交联型水性粘结剂的制备方法中步骤2)制备的混合溶液的溶质的质量比为70～95:2～20:3～10。
本发明还保护一种锂离子电池，所述锂离子电池包括电池壳、极芯和电解液，所述的极芯和电解液密封于电池壳内，所述的极芯包含上述的电极极片和位于电极极片之间的隔膜。
本发明的有益效果如下：
1)本发明提供的交联型水性粘结剂，能在水溶剂中应用，结合锂离子电池极片烘干工艺对浆料进行交联反应获得具有良好的弹性、粘结力和柔顺性的电极片，提供更多与电极活性材料接触的活性位点，大大地提高电解液中离子的传输速率，有利于电子/离子在充放电过程中的传导，能降低电化学界面阻抗。
2)本发明提供的交联型水性粘结剂应用于锂离子电池正负极，能提高电极浆料成膜时的均匀性和平整性，在烘干交联后增强活性物质、导电剂对金属基底的剥离强度，同时大大地增强电极活性物质、导电剂和集流体之间的粘结强度，较大改善了锂离子电池正负极材料循环稳定性能。
3)本发明提供的交联型水性粘结剂的制备方法简便，环保，合成的原料来源广泛，资源丰富，成本低，可以结合锂离子电池极片烘干工艺进行交联，无须另外的加工工艺条件，且获得具有良好粘结性、柔顺性、弹性的电极，解决现有技术中电极活性物质、导电剂和集流体之间的粘结强度不高，且不具有足够的弹性来缓解锂离子电池充、放电过程中的膨胀与收缩而松胀脱落的问题，具有广阔的市场前景，推动锂离子电池产业的技术进步。
4)本发明提供的交联型水性粘结剂克服了专利CN 104356979B中所得粘结剂的粘结力、分散性、弹性不足，且需要控制该粘结剂的交联度，否则不能起到粘接作用的缺点，而在极片的烘干过程中进行交联反应，可以得到分散更均匀，粘结力更强，提供更多与电极活性材料接触的活性位点的粘结剂。
附图说明：
图1-3是本发明实施例4-6 GA-PAA与含羟基、胺基等交联的红外图谱。
图4是本发明实施例7-9为GA-PAA与含羟基、胺基等作用的DSC实验。
图5是本发明实施例14PVA-PAA-MA与含羟基胺基交联的DSC实验。
图6是本发明实施例16为GA-PAA与含羟基胺基交联得到粘结剂用于Si负极材料循环性能测试。
图7是本发明实施例16硅负极及对比电极在电化学阻抗对比曲线。
图8为本发明实施例17 GA-PAA与含羟基胺基交联得到粘结剂用于LFP正极材料循环性能测试。
图9为本发明实施例17磷酸铁锂及对比电极的电化学阻抗对比曲线。
其中，阿拉伯胶记为GA；聚乙二醇记为PVA，季戊四醇记为PER，三乙醇胺记为TEOA，六甲氧甲基三聚氰胺记为HMMM，丙烯酸甲酯计为MA。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
阿拉伯胶记为GA；丙烯酸单体与阿拉伯胶经自由基接枝共聚反应或迈克尔加成反应改性制备的含有机羧酸基的水性高分子记为GA-PAA，聚乙二醇记为PVA，丙烯酸单体与聚乙二醇经自由基接枝共聚反应或迈克尔加成反应改性制备的含有机羧酸基的水性高分子记为PVA-PAA，丙烯酸甲酯，丙烯酸单体与聚乙二醇经自由基接枝共聚反应或迈克尔加成反应改性制备的含有机羧酸基的水性高分子记为PVA-PAA-MA，季戊四醇记为PER，三乙醇胺记为TEOA，六甲氧甲基三聚氰胺记为HMMM，丙烯酸甲酯计为MA。
以PVA-PAA为例，具体制备方法如：称取PVA于两口烧瓶，加入DI-water，在氩气气氛下搅拌使完全溶解，升温到65℃，依次加入Na2S2O8和NaHSO3的水溶液和丙烯酸单体，溶液在65℃、氩气气氛下反应48h，得到PVA-PAA水性高分子；所述引发剂的用量为单体总质量的0.01～5wt％。
以含有羟基阿拉伯胶GA和丙烯酸改性后含羧基的GA-PAA为例，含有羟基阿拉伯胶GA与含羧基水溶性小分子交联剂发生酯化的交联反应，反应结构式如下：
Figure PCTCN2017109004-appb-000001
丙烯酸改性后含羧基的GA-PAA与含羟基的水溶性小分子交联剂发生酯化的交联反应，反应结构式如下：
Figure PCTCN2017109004-appb-000002
实施例1：
GA-PAA与含羟基小分子交联的溶解性实验
(1)首先将1g GA-PAA(分子量为400000～1000000)，预先溶解于10ml去离子水(DI-Water)中，并在氩气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；搅拌速度为100～500转/分；
(2)将乙二醇、丙三醇、季戊四醇(OH:GA-PAA＝1:10摩尔比)一种或多种加到步骤(1)得到的溶液中，充分搅拌得到混合溶液；真空温度45℃，90℃,110℃条件下酯化反应1-24h，然后分别溶解在一定质量的水中，观察其溶解情况。
实施例2：
参考实施例1，不同之处在于步骤(2)：将三乙醇胺等含胺基小分子交联剂加入步骤(1)得到的溶液中，经过不同温度酰胺化反应，观察其溶解情况。
实施例3：
参考实施例1，不同之处在于步骤(2)：将六甲氧甲基三聚氰胺(HMMM)交联剂加入步骤(1)得到的溶液中，不同温度下酯化处理。观察其溶解情况。
由实施例1-3可知，GA-PAA在45-90℃能够完全溶解，加热到110℃以上会发生交联出现溶胀现象。当GA-PAA体系中加入季戊四醇(PER)、三乙醇胺(TEOA)或六甲氧甲基三聚氰胺(HMMM)时，45℃加热能够完全溶解，当温度升高到90℃或以上时会发生交联出现溶胀现象。
实施例4：
(1)首先将1g GA-PAA(分子量为400000～1000000)预先溶解于10ml去离子水 (DI-Water)中，并在氩气气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；搅拌速度为100～500转/分；
(2)将乙二醇、丙三醇、季戊四醇(OH:GA-PAA＝1:10摩尔比)一种或多种小分子加到步骤(1)得到的溶液中，充分搅拌得到混合溶液；在真空温度45℃，90℃,110℃条件下酯化反应24h，红外图谱参见图1。
实施例5：
参考实施例4，不同之处在于步骤(2)：将三乙醇胺等含胺基小分子加入步骤(1)得到的溶液中。红外光谱测试参见图2。
实施例6：
参考实施例4，不同之处在于步骤(2)：将六甲氧甲基三聚氰胺(HMMM)交联剂加入步骤(1)，不同温度下处理。其红外测试参见图3。
由图1-3可知，GA-PAA与季戊四醇(PER)、三乙醇胺(TEOA)或六甲氧甲基三聚氰胺，加热到110℃以上都发生交联反应。
实施例7：
(1)首先将1g GA-PAA(分子量为400000～1000000)预先溶解于10ml去离子水(DI-Water)中，并在氩气气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；搅拌速度为100～500转/分；
(2)将乙二醇、丙三醇、季戊四醇(OH:GA-PAA＝1:10摩尔比)一种或多种小分子加到步骤(1)得到的溶液中，充分搅拌得到混合溶液；在真空温度45℃条件下酯化反应24h。GA-PAA与含羟基交联的DSC实验图参见图4。
实施例8：
参考实施例7，不同之处在于步骤(2)：将三乙醇胺等含胺基小分子加入步骤(1)得到的溶液中进行酰胺化反应。图4是GA-PAA与含胺基交联的DSC实验。
实施例9：
参考实施例7，不同之处在于：将六甲氧甲基三聚氰胺等含胺基小分子加入步骤(1)得到的溶液中。图4是GA-PAA与含甲氧基交联的DSC实验。
由图4可知，GA-PAA与季戊四醇(PER)、三乙醇胺(TEOA)或六甲氧甲基三聚氰胺，加热到90℃以上都发生交联吸热反应。
实施例10：
交联型粘结剂剥离强度测试：
(1)首先将1g聚乙烯亚胺(PEI)(分子量为70000)预先溶解于10ml去离子水(DI-Water)中，并在氩气气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；搅拌速度为100～500转/分；
(2)丙二酸，丙三酸，己二酸一种或多种加到步骤(1)得到的溶液中，充分搅拌得到混合溶液；在真空温度45℃，90℃条件下反应1-24h，然后分别溶解在一定质量的水中，观察其溶解情况。可知，经过90°加热，PEI与上述不同交联剂发生交联反应。
(3)将(2)所得混合粘结剂，涂覆在Al箔上，涂覆厚度为100μm，110℃鼓风干燥，然后测试其剥离强度，测得剥离强度值为0.08N/mm。
实施例11：
参考实施例10，不同之处在于：步骤1)聚乙烯亚胺替换为含羟基水性高分子聚乙烯醇(PVA)，步骤(2)在真空温度45℃，110℃条件下反应1-24h，的，观察其溶解性实验。可知，经过110℃加热，PVA与上述不同交联剂发生交联反应。将所得混合粘结剂，涂覆在Al箔上，涂覆厚度为100μm，110℃鼓风干燥，然后测试其剥离强度，测得剥离强度值为0.10N/mm。
实施例12：
参考实施例1，不同之处在于：步骤1)GA-PAA替换为PVA-PAA，步骤(2)交联剂为季戊四醇(PER)，三乙醇胺(TEOA)，六甲氧甲基三聚氰胺(HMMM)的，观察其溶解性实验。
实施例13：
参考实施例12，不同之处在于：步骤1)PVA-PAA替换为PVA-PAA-MA，观察交联剂反应的溶解性实验。
实施例14：
参考实施例5，不同之处在于：加入反应底物为PVA-PAA-MA，其交联的DSC实验见图5。由图5可知，PVA-PAA-MA与季戊四醇(PER)，加热到90℃以上发生交联吸热反应。
实施例15：
电极的配制：
所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、粘结剂；且所述负极活性材料、导电剂和粘结剂的质量比70:20:10，所述溶剂为水。所述负极活性材料为硅；所述导电剂为乙炔黑；
所述集流体为铜箔集流体；所述锂离子电池负极浆料的固体含量为30％，锂离子电池负极浆料的粘度为3000mPa·s。制备得到GA-PAA-Si-负极剥离强度见表1。由表可知，经过不同交联剂交联，硅电极具有较高的剥离强度，其中GA-PAA-HMMM-Si的剥离强度最高达到0.28N/mm。
表1
电极片 剥离强度(N/mm)
GA-PAA-Si 0.18
GA-PAA-PER-Si 0.2
GA-PAA-HMMM-Si 0.28
GA-PAA-TEOA-Si 0.19
实施例16：
一、测试电极的配制：
本发明所述锂离子电池负极电极片的一种实施例，所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、粘结剂；且所述负极活性材料、导电剂和粘结剂的质量比70:20:10，所述溶剂为水。所述负极活性材料为硅；所述导电剂为乙炔黑；所述集流体为铜箔集流体；所述锂离子电池负极浆料的固体含量为75％，锂离子电池负极浆料的粘度为8000mPa·s。
将GA-PAA作为水性粘结剂原材料，溶解于去离子水中，并在保护性气氛氩气下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；再将季戊四醇(PER)，三乙醇胺(TEOA)，六甲氧甲基三聚氰胺(HMMM)交联剂中的任一种加入，搅拌均匀，GA-PAA与水溶性小分子交联剂的摩尔比为10:1，将硅和导电剂混合搅拌至均匀分散加入上述体系中，加适量去离子水调节粘度，用于制备锂离子硅负极材料浆料，得到硅电极浆料；将制得的浆料均匀涂覆于Cu箔上，110℃真空干燥，发生交联反应即得硅负极片。将真空干燥过的极片裁片称重后，将之在手套箱中组装在2025电池壳内，以锂片为对电极，以聚乙烯膜为隔膜，以1M LiPF6 EC/DMC/DEC(v/v/v＝1/1)为电解液组装电池进行恒电流充放电测试。
二、电化学测试：
对测试电极进行恒电流充放电的电化学性能测试和电化学阻抗测试。
四、结果分析：
图6为本实施例硅电极在400mA/g倍率下的循环性能测试曲线。从图中可以看出，采用三维交联改性高分子粘结剂制备的GA-PAA-TEOA-Si和GA-PAA-HMMM-Si负极，其拥有优良的循环性能，经过60次充放电循环后，其充电比容量高于1000mAh/g，远优于相同条件下的GA-PAA-Si，显示出优良的循环性能和电化学稳定性。可见，交联剂的加入能大大改进硅电极的循环稳定性。
图7硅负极及对比电极在电化学阻抗对比曲线。从图可以看出，采用三维交联改性高分子粘结剂制备的GA-PAA-TEOA-Si和GA-PAA-HMMM-Si负极，经过60次充放电循环后，其电化学阻抗小于相同条件下的GA-PAA-Si。可见，TEOA和HMMM交联剂的加入能减小硅电极的电化学阻抗。
实施例17：
一、测试电极的配制：
所述锂离子电池正电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂、粘结剂；且所述正极活性材料、导电剂和粘结剂的质量比95:2:3，所述溶剂为水。所述正极活性材料为LFP材料；所述导电剂为乙炔黑；所述集流体为铝箔集流体；所述锂离子电池正极浆料的固体含量为50％，锂离子电池正极浆料的粘度为5000mPa·s。
将GA-PAA作为为水性粘结剂原材料，溶解于去离子水中，并在保护性气氛氩气下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；加入上述体系中搅拌均匀，再将季戊四醇(PER)，三乙醇胺(TEOA)，六甲氧甲基三聚氰胺(HMMM)中的任一种交联剂加入，GA-PAA与水溶性小分子交联剂的摩尔比为10:0.1，搅拌均匀，将LFP和导电剂混合搅拌至均匀分散加入上述体系中，加适量去离子水调节粘度，用于制备得到LFP电极浆料；将制得的浆料均匀涂覆于Al箔上，110℃真空干燥发生交联反应，即得LFP电极片。将真空干燥过的极片裁片称重后，将之在手套箱中组装在2025电池壳内，以锂片为对电极，以聚乙烯膜为隔膜，以1M LiPF6EC/DMC/DEC(v/v/v＝1/1)为电解液组装电池进行恒电流充放电测试。
二、对比电极的配制：
采用GA-PAA作为粘结剂，按同样的方法配制对比电极。
三、电化学测试：
对测试电极、对比电极的充放电循环稳定性进行电化学测试和电化学阻抗测试。
四、结果分析：
图8为本实施例测试LFP电极及对比电极在0.5C充放电电流密度下的循环性能测试曲线。采用三维交联改性GA-PAA基高分子锂离子电池粘结剂制备的LFP电极，都具有较好的循环稳定性。与GA-PAA-LFP电极相比，GA-PAA-PER-LFP电极具有较高的比容量，经过50次充放电循环后，GA-PAA-LFP，GA-PAA-PER-LFP，GA-PAA-HMMM-LFP，GA-PAA-TEOA-LFP电极的比容量分别为135.6，142.9，127和132mAh/g。可见交联剂PER的加入能提高LFP电极的比容量和循环稳定性。
图9中LFP电极及对比电极的电化学阻抗对比曲线。从图可以看出，与GA-PAA-LFP电极相比，经过50次充放电循环后，GA-PAA-PER-LFP电极表现了较低的电化学阻抗。交联基PER的加入能提高LFP电极电化学性能。

Claims (10)

  1. 一种锂离子电池交联型水性粘结剂的制备方法，其特征在于，由含有机羧酸或氨基或羟基的水性高分子与含有羟基、胺基或羧基的水溶性小分子交联剂共同作为水性粘结剂原材料，在锂离子电池电极片浆料涂布烘干条件下经酯化、酰胺化反应交联，所述含有机羧酸或氨基或羟基的水性高分子的分子量为70000～1000000，所述含有机羧酸基的水性高分子由丙烯酸单体与含羟基的水性高分子经自由基接枝共聚反应或迈克尔加成反应改性制备获得，其中，含羟基的水性高分子选自阿拉伯胶、环糊精、纤维素衍生物、黄原胶、果胶、明胶、淀粉、田菁胶、聚乙烯醇、聚乙二醇、多羟基聚丁二烯中的一种或两种以上；所述含氨基水性高分子选自阿拉伯胶、壳聚糖及其衍生物、线性聚乙烯亚胺、支链聚乙烯亚胺中的一种或两种以上；该方法包括以下步骤：
    1)将含有机羧酸或氨基或羟基的水性高分子溶解于去离子水中，并在保护性气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；
    2)将含有羟基、胺基或羧基的水溶性小分子交联剂加到步骤1)得到的溶液中，充分搅拌得到均匀的混合溶液；含有羟基、胺基或羧基的水溶性小分子交联剂与含有机羧酸或氨基或羟基的水性高分子摩尔比为0.01:10～1:10；
    3)将步骤2)制备的混合溶液90-130℃进行交联反应得到目标粘结剂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤3)中将步骤2)制备的混合溶液用于制备锂离子正、负极材料浆料，其浆料涂覆集流体后在烘干过程中交联剂进行交联反应得到目标粘结剂，烘干温度为90～110℃。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述含羟基水溶性小分子交联剂具有如下结构单体中的至少一种：碳原子数大于等于2的饱和二元醇、碳原子数大于等于3的饱和多元醇、饱和二元醇胺NH-(CmH2m-OH)2、饱和多元醇胺N-(Cm’H2m’-OH)3，其中m≥1，m’≥1；所述含胺基水溶性小分子交联剂具有如下结构单体中的至少一种：饱和二元胺CnH2n(NH2)2、饱和多元胺Cn’H2n’+2-x(NH2)x，其中n≥2，n’≥3，x≥3；所述含羧基水溶性小分子交联剂具有如下结构单体中的至少一种：饱和二元酸、碳原子数大于等于3的饱和多元酸。
  4. 根据权利要求1或2所述的制备方法，其特征在于，所述含有羟基、胺基或羧基的水溶性小分子交联剂选自乙二醇、丙三醇、季戊四醇、乙二醇胺、三乙醇胺、六甲氧甲基三聚氰胺、己二酸、丙二酸，丙三酸的一种或两种以上。
  5. 根据权利要求1或2所述的制备方法，其特征在于，步骤1)所述保护性气氛为氮 气和/或氩气，所述搅拌速度为100～500转/分；步骤2)含有羟基、胺基或羧基的水溶性小分子交联剂与含有机羧酸或氨基或羟基的水性高分子摩尔比0.5:10-1:10。
  6. 一种锂离子电池交联型水性粘结剂，其特征在于，利用权利要求1-5中任一权利要求所述的制备方法制备得到。
  7. 权利要求6所述的锂离子电池交联型水性粘结剂在电化学储能器件中的应用，所述电化学储能器件包括锂离子电池、二次电池、超级电容器、太阳能电池。
  8. 根据权利要求7所述的应用，其特征在于，应用在锂离子电池的正极片中；所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂和权利要求1中步骤2)制备的混合溶液，所述锂离子电池正极浆料的固体含量为30～75％，锂离子电池正极浆料的粘度为3000～8000mPa·s，锂离子电池正极浆料涂覆集流体后烘干得到目标电极；所述正极活性材料选自磷酸铁锂、钴酸锂、锰酸锂或NMC三元材料的一种或多种；所述导电剂为乙炔黑；所述集流体为铝箔；正极活性材料、导电剂和权利要求1中步骤2)制备的混合溶液的溶质的质量比为70～95:2～20:3～10。
  9. 根据权利要求7所述的应用，其特征在于，应用在锂离子电池的负极片中；所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂和权利要求1中步骤2)制备的混合溶液，所述锂离子电池负极浆料的固体含量为30～75％，锂离子电池负极浆料的粘度为3000～8000mPa·s，锂离子电池负极浆料涂覆集流体后烘干得到目标电极；所述负极活性材料选自硅基材料、钛酸锂或石墨的一种或两种以上；所述导电剂为乙炔黑；集流体为铜箔；负极活性材料、导电剂和权利要求1中步骤2)制备的混合溶液的溶质的质量比为70～95:2～20:3～10。
  10. 一种锂离子电池，所述锂离子电池包括电池壳、极芯和电解液，所述的极芯和电解液密封于电池壳内，其特征在于，所述的极芯包含权利要求8或9得到的电极极片和位于电极极片之间的隔膜。
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