CN115050963B - Adhesive for negative electrode of lithium ion battery, and preparation method and application thereof - Google Patents
Adhesive for negative electrode of lithium ion battery, and preparation method and application thereof Download PDFInfo
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- CN115050963B CN115050963B CN202210764529.5A CN202210764529A CN115050963B CN 115050963 B CN115050963 B CN 115050963B CN 202210764529 A CN202210764529 A CN 202210764529A CN 115050963 B CN115050963 B CN 115050963B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 239000000853 adhesive Substances 0.000 title claims description 13
- 230000001070 adhesive effect Effects 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims description 189
- 239000000178 monomer Substances 0.000 claims description 62
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 36
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 150000001491 aromatic compounds Chemical class 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 150000001993 dienes Chemical class 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 239000011258 core-shell material Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- YHOHCZWPIKTKAZ-UHFFFAOYSA-N dihexyl butanedioate;sodium Chemical compound [Na].CCCCCCOC(=O)CCC(=O)OCCCCCC YHOHCZWPIKTKAZ-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- BXXJYCDMABTQHF-UHFFFAOYSA-N C(C=C)(=O)N.C(C=C)(=O)N.C(C(O)C(O)C(=O)O)(=O)O Chemical compound C(C=C)(=O)N.C(C=C)(=O)N.C(C(O)C(O)C(=O)O)(=O)O BXXJYCDMABTQHF-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZMLXKXHICXTSDM-UHFFFAOYSA-N n-[1,2-dihydroxy-2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NC(O)C(O)NC(=O)C=C ZMLXKXHICXTSDM-UHFFFAOYSA-N 0.000 claims description 2
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002313 adhesive film Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of high polymer materials, in particular to a binder for a negative electrode of a lithium ion battery, a method for preparing the binder for the negative electrode of the lithium ion battery, the binder prepared by the method, the negative electrode containing the binder and the lithium ion battery containing the negative electrode. Through the technical scheme, the binder for the lithium ion battery cathode can have excellent electrolyte tolerance after film formation, so that the performance of the lithium ion battery can be effectively improved.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a binder for a negative electrode of a lithium ion battery, a method for preparing the binder for the negative electrode of the lithium ion battery, the binder prepared by the method, the negative electrode containing the binder and the lithium ion battery containing the negative electrode.
Background
The lithium ion battery has the advantages of high voltage, large specific energy, stable discharge voltage, good cycle performance, excellent safety performance, long storage and working life and the like, and is one of the latest development directions of the current chemical power supply industry.
The main material of the negative electrode of the lithium ion secondary battery is powder, wherein graphite and conductive agent carbon black are nonpolar and surface hydrophobic substances, and are easy to aggregate in water and difficult to disperse. The electrode must therefore be prepared using suitable additives, typically including stabilizers (e.g., CMC) and binders (e.g., SBR). On one hand, the SBR is combined with graphite and carbon black as a conductive agent through a hydrophobic group, and on the other hand, a condensation reaction is carried out through a hydrophilic group and a group on the surface of a current collector, so that CMC has an auxiliary bonding effect on the SBR, and meanwhile, the SBR can be dispersed more uniformly, and meanwhile, the stability of the whole system is ensured by utilizing the repulsive interaction of space charges.
The manufacturing method and the application environment of the secondary battery are complex, more inorganic matters and organic matters exist in the secondary battery, the secondary battery is externally influenced by factors such as use environment, artificial influence and the like, and the working condition environment is poor. Particularly, electrolyte is added in the manufacturing process of the secondary battery, so that the SBR is in a state of being soaked in the electrolyte for a long time in the battery, and the adhesion degree and the tolerance degree of the SBR and a current collector are deteriorated under the influence of working conditions such as high and low temperature, cyclic charge and discharge, high-current charge and discharge and the like of the secondary battery.
Therefore, the conventional SBR has a defect that it is difficult to have excellent electrolyte resistance.
Disclosure of Invention
The invention aims to provide a binder for a lithium ion battery anode, which is extremely excellent in electrolyte tolerance.
In order to achieve the above object, the present invention provides a binder for a negative electrode of a lithium ion battery, the binder comprising a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 0.05-50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; the comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
The invention also provides a method for preparing the binder for the negative electrode of the lithium ion battery, which comprises the following steps: carrying out first emulsion polymerization on a comonomer in a first nuclear copolymer zone to obtain a first nuclear copolymer; performing second emulsion polymerization on the first core copolymer and a comonomer of a first shell copolymer region to obtain a first copolymer with a first core-shell structure; carrying out third emulsion polymerization on the comonomer in the second nuclear copolymer zone to obtain a second nuclear copolymer; carrying out fourth emulsion polymerization on the second core copolymer and a comonomer of a second shell copolymer region to obtain a second copolymer with a second core-shell structure; mixing the first copolymer and the second copolymer according to the weight ratio of 0.05-50:1; the comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
The invention also provides the adhesive prepared by the method.
The invention also provides application of the binder in preparation of a lithium ion battery negative electrode.
The invention also provides a lithium ion battery cathode which contains the binder.
The invention also provides a lithium ion battery, which comprises a positive electrode, electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
Through the technical scheme, the binder for the lithium ion battery cathode can have excellent electrolyte tolerance after film formation, so that the performance of the lithium ion battery can be effectively improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
fig. 1 is a photograph of the second adhesive film of example 1, and fig. 2 is a photograph of the first adhesive film of example 1. Fig. 3 is a photograph of the second adhesive film of comparative example 1, and fig. 4 is a photograph of the first adhesive film of comparative example 1.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a binder for a lithium ion battery cathode, which comprises a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 0.05-50:1; the first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; the comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
The invention is characterized in that: the first copolymer has lower glass transition temperature, higher binding power, higher elastic modulus after film formation and electrolyte tolerance, the second copolymer has lower glass transition temperature, higher binding power and higher breaking tensile force, and the adhesive obtained after the two are compounded has good adhesive film elastic modulus, low battery internal resistance, high cycle capacity retention rate, and better high-low temperature performance and processability.
Wherein, in order to make the binder have better performance, the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1.
The weight ratio of the first core copolymer region to the first shell copolymer region is from 0.01 to 20:1, preferably from 0.1 to 10:1, more preferably from 0.3 to 5:1; in the second copolymer, the weight ratio of the second core copolymer region to the second shell copolymer region is 0.01 to 50:1, preferably 0.1 to 30:1, more preferably 0.3 to 5:1.
Optionally, the polymer particles of the first copolymer have a particle size between 50-1000nm, and the first copolymer has a glass transition temperature of-40 ℃ to 90 ℃; the particle size of the polymer particles of the second copolymer is 50-1000nm, and the glass transition temperature of the second copolymer is-40 ℃ to 90 ℃; the binder has a solids content of 10 to 60% by weight.
Optionally, wherein each of the monovinylaromatic compounds is independently at least one of styrene, ortho-methylstyrene, meta-methylstyrene, and para-methylstyrene; the aliphatic conjugated dienes are each independently 1, 3-butadiene and/or isoprene; the water-soluble unsaturated carboxylic acids are each independently at least one of methacrylic acid, acrylic acid, itaconic acid, fumaric acid, and maleic acid; the bisacrylamide monomers are at least one of N, N-methylene bisacrylamide, N- (1, 2-dihydroxyethylene) bisacrylamide and tartaric acid bisacrylamide respectively and independently; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate.
Preferably, the monovinylaromatic compound is styrene, the aliphatic conjugated diene is 1, 3-butadiene, the water-soluble unsaturated carboxylic acid in the first core copolymer zone, the first shell copolymer zone, and the second core copolymer zone is itaconic acid, the water-soluble unsaturated carboxylic acid in the second shell copolymer zone is acrylic acid and/or methacrylic acid, the bisacrylamide monomer is N, N-methylenebisacrylamide, and the acrylate monomer is butyl acrylate. The butyl acrylate may be n-butyl acrylate and/or isobutyl acrylate.
The invention also provides a method for preparing the binder for the negative electrode of the lithium ion battery, which comprises the following steps: carrying out first emulsion polymerization on a comonomer in a first nuclear copolymer zone to obtain a first nuclear copolymer; performing second emulsion polymerization on the first core copolymer and a comonomer of a first shell copolymer region to obtain a first copolymer with a first core-shell structure; carrying out third emulsion polymerization on the comonomer in the second nuclear copolymer zone to obtain a second nuclear copolymer; carrying out fourth emulsion polymerization on the second core copolymer and a comonomer of a second shell copolymer region to obtain a second copolymer with a second core-shell structure; the first copolymer and the second copolymer are mixed according to the weight ratio of 0.05-50:1.
Wherein the comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinylaromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
Optionally, the weight ratio of the first copolymer to the second copolymer is preferably 0.5-15:1, preferably 2-8:1, more preferably 4.5-5.5:1, and most preferably 4.89:1.
Optionally, wherein the conditions of the first emulsion polymerization comprise: the total concentration of the comonomers in the first core copolymer zone is 1-30 wt%, the concentration of the emulsifier is 0.01-10 wt%, the concentration of the molecular weight regulator is 0.001-5 wt%, the concentration of the initiator is 0.001-20 wt%, the concentration of the chelating agent is 0.01-10 wt%, the polymerization time is 1-1000 min, and the polymerization temperature is 30-90 ℃.
Optionally, wherein the conditions of the second emulsion polymerization comprise: the amount of the material obtained after the first emulsion polymerization is 0.1 to 90% by weight, the total concentration of the comonomer in the first shell copolymer region is 1 to 30% by weight, the concentration of the emulsifier is 0.01 to 10% by weight, the concentration of the molecular weight regulator is 0.001 to 5% by weight, the concentration of the initiator is 0.001 to 20% by weight, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃.
Optionally, wherein the conditions of the third emulsion polymerization include: the total concentration of the comonomers in the second core copolymer zone is 0.1 to 90 wt%, the concentration of the emulsifier is 0.001 to 20 wt%, the concentration of the molecular weight regulator is 0.001 to 20 wt%, the concentration of the initiator is 0.001 to 20 wt%, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃.
Optionally, wherein the conditions of the fourth emulsion polymerization comprise: the amount of the material obtained after the third emulsion polymerization is 1 to 85% by weight, the total concentration of the comonomer in the second shell copolymer region is 1 to 30% by weight, the concentration of the emulsifier is 0.001 to 20% by weight, the concentration of the molecular weight regulator is 0.001 to 20% by weight, the concentration of the initiator is 0.001 to 20% by weight, the concentration of the chelating agent is 0.01 to 10% by weight, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃.
Optionally, wherein the emulsifiers are each independently selected from at least one of sodium dihexyl succinate sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol ether sulfate, dodecylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, sodium secondary alkyl sulfonate, alkyl diphenyl ether disulfonate, and aliphatic carboxylate; the molecular weight regulators are each independently selected from at least one of n-dodecyl mercaptan, t-dodecyl mercaptan, diisopropyl xanthogen disulfide and alpha-methyl styrene linear dimer.
The invention also provides the adhesive prepared by the method.
The invention also provides application of the binder in preparation of a lithium ion battery negative electrode.
The invention also provides a lithium ion battery cathode which contains the binder.
The invention also provides a lithium ion battery, which comprises a positive electrode, electrolyte and a negative electrode; the negative electrode is the negative electrode as described above.
The invention is illustrated in further detail by the following examples. The starting materials used in the examples are all available commercially.
Example 1
And (3) carrying out first emulsion polymerization on the comonomer in the first nuclear copolymer zone to obtain the first nuclear copolymer. Wherein the comonomers of the first core copolymer zone comprise 2.8 parts by weight styrene, 4.03 parts by weight butadiene, 0.28 parts by weight itaconic acid, and 0.88 parts by weight N, N-methylenebisacrylamide.
The conditions of the first emulsion polymerization include: the total concentration of the comonomers in the first core copolymer zone was 9.24 wt%, the emulsifier (1:2.114 mixture of sodium dihexyl sulfosuccinate and sodium dodecylbenzenesulfonate) was 2.1 wt%, the molecular weight regulator (t-dodecyl mercaptan) was 0.027 wt%, the initiator (ammonium persulfate) was 5.4 wt%, the chelating agent (EDTA) was 0.054 wt%, the balance was made up with water, the polymerization time was 10 minutes, and the polymerization temperature was 68 ℃.
And (3) carrying out second emulsion polymerization on the first core copolymer (used as a material obtained after the first emulsion polymerization) and a comonomer in a first shell copolymer area to obtain a first copolymer with a first core-shell structure.
The comonomers of the first shell copolymer zone included 37.2 parts by weight styrene, 53.53 parts by weight butadiene, 1.12 parts by weight itaconic acid, and 0.22 parts by weight N, N-methylenebisacrylamide.
The conditions of the second emulsion polymerization include: the amount of material obtained after the first emulsion polymerization was 77.40% by weight, the amount of comonomer in the first shell copolymer zone was 10.58% by weight, the concentration of the emulsifier (1:1.158 mixture of sodium dihexyl succinate sulfonate and sodium dodecylbenzenesulfonate) was 0.186% by weight, the concentration of the molecular weight regulator (t-dodecyl mercaptan) was 0.239% by weight, the concentration of the initiator (ammonium persulfate) was 3.98% by weight, the balance was made up with water, the polymerization time was 630 minutes, and the polymerization temperature was 68 ℃. After the polymerization is completed, a second copolymer is obtained.
And carrying out third emulsion polymerization on the comonomer in the second core copolymer region to obtain the second core copolymer.
The comonomers of the second core copolymer zone comprise 8.575 parts by weight styrene, 25.725 parts by weight butyl acrylate, and 3 parts by weight itaconic acid;
the conditions of the third emulsion polymerization include: the total concentration of the comonomer of the second core copolymer zone was 6.63 wt%, the concentration of the emulsifier (dodecylphenol polyoxyethylene ether) was 0.58 wt%, the concentration of the molecular weight regulator (n-dodecylmercaptan) was 0.066 wt%, the concentration of the initiator (ammonium persulfate) was 3.86 wt%, the balance was made up with water, the polymerization time was 15 minutes, and the polymerization temperature was 69 ℃.
And (3) carrying out fourth emulsion polymerization on the second core copolymer (used as a material obtained after the third emulsion polymerization) and a comonomer in a second shell copolymer area to obtain a second copolymer with a second core-shell structure.
The comonomers of the second shell copolymer zone included 111 parts by weight styrene, 9.5 parts by weight butyl acrylate, 333 parts by weight acrylic acid, and 11.1 parts by weight N, N-methylenebisacrylamide.
The conditions of the fourth emulsion polymerization include: the amount of the material obtained after the third emulsion polymerization was 56.93% by weight, the amount of the comonomer in the second shell copolymer region was 7.49% by weight, the concentration of the emulsifier (fatty alcohol ether sulfate) was 0.29% by weight, the concentration of the molecular weight regulator (n-dodecyl mercaptan) was 0.086% by weight, the concentration of the initiator (ammonium persulfate) was 4.5% by weight, the concentration of the chelating agent (EDTA) was 4.5% by weight, the balance was made up with water, the polymerization time was 510 minutes, and the polymerization temperature was 69 ℃. After the polymerization is completed, a second copolymer is obtained.
The first copolymer and the second copolymer were mixed at a weight ratio of 4.89:1, and the solid content was adjusted to 40% by weight, to obtain the adhesive of this example.
Example 2
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a weight ratio of 8:1.
Example 3
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a weight ratio of 2:1.
Example 4
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a weight ratio of 15:1.
Example 5
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a weight ratio of 0.5:1.
Example 6
A binder was prepared as in example 1; the difference is that: the itaconic acid in the first copolymer is replaced with acrylic acid.
Example 7
A binder was prepared as in example 1; the difference is that: the itaconic acid in the first copolymer is replaced with fumaric acid.
Example 8
A binder was prepared as in example 1; the difference is that: the itaconic acid in the first copolymer is replaced with maleic acid.
Example 9
A binder was prepared as in example 1; the difference is that: butyl acrylate in the second copolymer is replaced with ethyl acrylate.
Example 10
A binder was prepared as in example 1; the difference is that: and (3) replacing the acrylic acid in the second copolymer with itaconic acid.
Comparative example 1
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a 60:1 weight ratio.
Comparative example 2
A binder was prepared as in example 1; the difference is that: the first copolymer and the second copolymer were mixed in a weight ratio of 0.04:1.
Comparative example 3
A binder was prepared as in example 1; the difference is that: the itaconic acid in the first copolymer is replaced with acrylamide.
Comparative example 4
A binder was prepared as in example 1; the difference is that: the butyl acrylate in the second copolymer is replaced with acrylamide.
Test example 1
This test example the binders of examples 1-10 and comparative examples 1-4 were tested for resistance to immersion in electrolyte.
70G of binder diluted to 20 weight percent of solid content is taken, poured into a mould and transferred to an oven, baked for 8 hours at 60 ℃ and 4 hours at 90 ℃, baked for 2 hours at 120 ℃ and baked for 15 minutes at 140 ℃ to obtain the adhesive film. And then punching the adhesive film into a dumbbell shape to serve as a first adhesive film for standby. And placing the first adhesive film into an aluminum plastic bag, injecting electrolyte with 40 times of the weight of the adhesive film, and sealing. And (5) transferring the packaged aluminum-plastic bag into a baking oven at 40 ℃ and baking for 15 days. Taking out the plastic-aluminum bag inner adhesive film, and using the absorbent paper to absorb electrolyte on the surface of the adhesive film as a second adhesive film for standby. And baking the second adhesive film in a baking oven at 140 ℃ for 2 hours, and drying residual electrolyte in the adhesive film to serve as a third adhesive film for standby.
The first, second and third films were subjected to a stretching experiment, and the results are shown in tables 1 to 3. Fig. 1 is a photograph of the second adhesive film of example 1, and fig. 2 is a photograph of the first adhesive film of example 1. Fig. 3 is a photograph of the second adhesive film of comparative example 1, and fig. 4 is a photograph of the first adhesive film of comparative example 1. It is evident that the film of comparative example 1 was brown in color after electrolyte soaking, whereas the film of example 1 was not significantly changed in color after electrolyte soaking. The adhesive film of example 1 is thus demonstrated to have excellent electrolyte immersion resistance.
TABLE 1 first adhesive film test results
TABLE 2 second adhesive film test results
TABLE 3 third adhesive film test results
As can be seen from the results of tables 1 to 3, the adhesive film formed by the adhesive of the present invention is less affected by the immersion of the electrolyte.
Test example 2
This test example peel strength (collector adhesion) was tested for the adhesives of examples 1-10 and comparative examples 1-4.
The invention is added into the cathode slurry according to the addition amount of 1.4 weight percent and 1.7 weight percent, then the pole piece is obtained after pulping, coating, drying and rolling, the pole piece is punched into 20mm wide strips, and the test is carried out on a universal tensile testing machine by adopting a 90-degree stripping method. The results are shown in Table 4.
Table 4 peel strength test results
As can be seen from the results of table 4, the adhesive of the present invention has a high peel strength after curing.
Test example 3
This test example batteries were prepared with the binders of examples 1-10 and comparative examples 1-4 and tested for battery cycle performance.
The battery is evaluated by using a soft package lamination 5AH, a positive electrode is a capacity type LFP, a negative electrode is similar to FSN artificial graphite, CMC addition amount is 1.2%, and the battery design is tested by referring to an energy type battery design method at normal temperature 1C and at the temperature of 55 ℃ for 110 weeks. The results are shown in Table 5.
Table 5 battery cycle performance test results
As can be seen from the results of table 5, the prepared battery of the binder of the present invention has good cycle performance.
As can be seen from the above test examples, the binder for a negative electrode of a lithium ion battery according to the present invention can have excellent electrolyte tolerance after film formation, so that the performance of the lithium ion battery can be effectively improved, and particularly, the binder has better performance in the case that the weight ratio of the first copolymer to the second copolymer is preferably 0.5 to 15:1, preferably 2 to 8:1, more preferably 4.5 to 5.5:1.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (14)
1. A binder for a negative electrode of a lithium ion battery, the binder comprising a first copolymer and a second copolymer; the weight ratio of the first copolymer to the second copolymer is 2-8:1;
The first copolymer has a first core-shell structure and contains a first core copolymer region and a first shell copolymer region; the comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer;
The second copolymer has a second core-shell structure and contains a second core copolymer region and a second shell copolymer region; the comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
2. The adhesive of claim 1, wherein the weight ratio of the first copolymer to the second copolymer is 4.5-5.5:1;
in the first copolymer, the weight ratio of the first core copolymer region to the first shell copolymer region is 0.01-20:1;
in the second copolymer, the weight ratio of the second core copolymer region to the second shell copolymer region is 0.01-50:1.
3. The adhesive of claim 2 wherein the weight ratio of the first core copolymer region to the first shell copolymer region in the first copolymer is from 0.1 to 10:1;
In the second copolymer, the weight ratio of the second core copolymer region to the second shell copolymer region is 0.1 to 30:1.
4. The adhesive of claim 3 wherein the weight ratio of the first core copolymer region to the first shell copolymer region in the first copolymer is from 0.3 to 5:1;
in the second copolymer, the weight ratio of the second core copolymer region to the second shell copolymer region is 0.3-5:1.
5. The binder of claim 1, wherein the polymer particles of the first copolymer have a particle size between 50-1000nm and a glass transition temperature of-40 ℃ to 90 ℃;
The particle size of the polymer particles of the second copolymer is 50-1000nm, and the glass transition temperature of the second copolymer is-40 ℃ to 90 ℃;
The binder has a solids content of 10 to 60% by weight.
6. The adhesive according to any one of claims 1 to 5, wherein the monovinyl aromatic compounds are each independently at least one of styrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene; the aliphatic conjugated dienes are each independently 1, 3-butadiene and/or isoprene; the water-soluble unsaturated carboxylic acids are each independently at least one of methacrylic acid, acrylic acid, itaconic acid, fumaric acid, and maleic acid; the bisacrylamide monomers are at least one of N, N-methylene bisacrylamide, N- (1, 2-dihydroxyethylene) bisacrylamide and tartaric acid bisacrylamide respectively and independently; the acrylic ester monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and amyl acrylate.
7. The binder of claim 6 wherein the monovinylaromatic compound is styrene, the aliphatic conjugated diene is 1, 3-butadiene, the water-soluble unsaturated carboxylic acid in the first core copolymer region, the first shell copolymer region, and the second core copolymer region is itaconic acid, the water-soluble unsaturated carboxylic acid in the second shell copolymer region is acrylic acid and/or methacrylic acid, the bisacrylamide monomer is N, N-methylenebisacrylamide, and the acrylate monomer is butyl acrylate.
8. A method of preparing a binder for a negative electrode of a lithium ion battery, the method comprising:
Carrying out first emulsion polymerization on a comonomer in a first nuclear copolymer zone to obtain a first nuclear copolymer;
Performing second emulsion polymerization on the first core copolymer and a comonomer of a first shell copolymer region to obtain a first copolymer with a first core-shell structure;
carrying out third emulsion polymerization on the comonomer in the second nuclear copolymer zone to obtain a second nuclear copolymer;
Carrying out fourth emulsion polymerization on the second core copolymer and a comonomer of a second shell copolymer region to obtain a second copolymer with a second core-shell structure;
mixing the first copolymer and the second copolymer according to the weight ratio of 2-8:1;
The comonomer of the first core copolymer zone comprises 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 20 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer; the comonomers of the first shell copolymer zone comprise 1 to 60 parts by weight of a monovinyl aromatic compound, 1 to 100 parts by weight of an aliphatic conjugated diene, 0.01 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.01 to 20 parts by weight of a bisacrylamide monomer;
The comonomers of the second core copolymer zone comprise 0.1 to 20 parts by weight of a monovinyl aromatic compound, 0.1 to 50 parts by weight of an acrylate monomer, and 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer; the comonomers of the second shell copolymer zone comprise 0.1 to 200 parts by weight of a monovinylaromatic compound, 0.1 to 500 parts by weight of an acrylate monomer, 0.1 to 20 parts by weight of a water-soluble unsaturated carboxylic acid monomer, and 0.1 to 20 parts by weight of a bisacrylamide monomer.
9. The method of claim 8, wherein the weight ratio of the first copolymer to the second copolymer is 4.5-5.5:1.
10. The method of claim 8, wherein,
The conditions of the first emulsion polymerization include: the total concentration of the comonomer in the first core copolymer zone is 1-30 wt%, the concentration of the emulsifier is 0.01-10 wt%, the concentration of the molecular weight regulator is 0.001-5 wt%, the concentration of the initiator is 0.001-20 wt%, the concentration of the chelating agent is 0.01-10 wt%, the polymerization time is 1-1000 minutes, and the polymerization temperature is 30-90 ℃;
the conditions of the second emulsion polymerization include: the material obtained after the first emulsion polymerization is used in an amount of 0.1 to 90 wt%, the total concentration of the comonomer in the first shell copolymer region is 1 to 30 wt%, the concentration of the emulsifier is 0.01 to 10wt%, the concentration of the molecular weight regulator is 0.001 to 5wt%, the concentration of the initiator is 0.001 to 20 wt%, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃;
The conditions of the third emulsion polymerization include: the total concentration of the comonomer in the second core copolymer zone is 0.1 to 90 wt%, the concentration of the emulsifier is 0.001 to 20 wt%, the concentration of the molecular weight regulator is 0.001 to 20 wt%, the concentration of the initiator is 0.001 to 20 wt%, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃;
The conditions of the fourth emulsion polymerization include: the material obtained after the third emulsion polymerization is used in an amount of 1 to 85 weight percent, the total concentration of the comonomer in the second shell copolymer region is 1 to 30 weight percent, the concentration of the emulsifier is 0.001 to 20 weight percent, the concentration of the molecular weight regulator is 0.001 to 20 weight percent, the concentration of the initiator is 0.001 to 20 weight percent, the concentration of the chelating agent is 0.01 to 10 weight percent, the polymerization time is 1 to 1000 minutes, and the polymerization temperature is 30 to 90 ℃;
The emulsifier is at least one of sodium dihexyl succinate sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol ether sulfate, dodecyl phenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, secondary alkyl sodium sulfonate, alkyl diphenyl ether disulfonate and aliphatic carboxylate respectively and independently;
the molecular weight regulators are each independently selected from at least one of n-dodecyl mercaptan, t-dodecyl mercaptan, diisopropyl xanthogen disulfide and alpha-methyl styrene linear dimer;
The initiator is at least one of potassium persulfate, sodium persulfate, ammonium persulfate, tertiary butyl hydroperoxide, benzoyl peroxide and acetylated hydrogen peroxide.
11. A binder prepared according to the method of any one of claims 8-10.
12. Use of a binder according to any one of claims 1-7 and 11 in the preparation of a negative electrode for a lithium ion battery.
13. A lithium ion battery negative electrode, characterized in that the lithium ion battery negative electrode contains the binder according to any one of claims 1-7 and 11.
14. A lithium ion battery, characterized in that the lithium ion battery comprises a positive electrode, an electrolyte and a negative electrode; the negative electrode according to claim 13.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664001A (en) * | 2000-09-21 | 2005-09-07 | 罗姆和哈斯公司 | Aqueous nanocomposite dispersions: processes, compositions, and uses thereof |
| CN103173161A (en) * | 2013-03-08 | 2013-06-26 | 东莞新能源科技有限公司 | Preparation method of lithium ion battery cathode sheet adhesive emulsion |
| JP2014203805A (en) * | 2013-04-10 | 2014-10-27 | 日本ゼオン株式会社 | Particulate binder for lithium ion secondary battery negative electrode, slurry composition for lithium ion secondary battery negative electrode, and lithium ion secondary battery |
| WO2015160794A1 (en) * | 2014-04-14 | 2015-10-22 | Ecosynthetix Ltd. | Bio-based nanoparticle and composite materials derived therefrom |
| KR101698745B1 (en) * | 2015-08-03 | 2017-01-23 | 주식회사 한솔케미칼 | Core-shell structured binders for use of anode materials of lithium ion secondary battery and method for preparing using the same, and slurry comprising said binders |
| WO2017056466A1 (en) * | 2015-09-28 | 2017-04-06 | 日本ゼオン株式会社 | Binder composition for nonaqueous secondary battery electrodes, slurry composition for nonaqueous secondary battery electrodes, electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN108929401A (en) * | 2018-06-25 | 2018-12-04 | 重庆云天化瀚恩新材料开发有限公司 | A kind of lithium battery silicium cathode adhesive and preparation method thereof |
| CN113228397A (en) * | 2018-12-28 | 2021-08-06 | 三星Sdi株式会社 | Separator for lithium secondary battery and lithium secondary battery including the same |
| CN113555558A (en) * | 2021-07-12 | 2021-10-26 | 珠海冠宇电池股份有限公司 | Emulsion type binder and lithium ion battery comprising same |
| CN114520329A (en) * | 2020-11-19 | 2022-05-20 | 比亚迪股份有限公司 | Adhesive, preparation method thereof and slurry |
| KR20220087853A (en) * | 2020-12-18 | 2022-06-27 | 주식회사 엘지화학 | Electrode binder composition for rechargeable battery and electrode mixture including the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101597745B1 (en) * | 2013-05-23 | 2016-02-25 | 주식회사 엘지화학 | Binder for Secondary Battery and Secondary Battery Comprising the Same |
| CN106663813B (en) * | 2014-09-05 | 2020-12-08 | 日本瑞翁株式会社 | Binder composition for secondary battery electrode, slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
| KR101953765B1 (en) * | 2015-06-17 | 2019-06-12 | 주식회사 엘지화학 | Binder Composition for Secondary Battery, and Electrode Employed with the Same, and Lithium Secondary Battery |
| CN111825804B (en) * | 2020-07-27 | 2022-03-29 | 日照广大建筑材料有限公司 | Copolymer latex for lithium ion secondary battery cathode, preparation method and application |
| CN114583173A (en) * | 2022-03-15 | 2022-06-03 | 湖北亿纬动力有限公司 | Negative electrode slurry composition and application |
| CN115050963B (en) * | 2022-06-29 | 2024-05-10 | 上海道赢实业有限公司 | Adhesive for negative electrode of lithium ion battery, and preparation method and application thereof |
-
2022
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-
2023
- 2023-06-28 WO PCT/CN2023/103478 patent/WO2024002199A1/en unknown
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664001A (en) * | 2000-09-21 | 2005-09-07 | 罗姆和哈斯公司 | Aqueous nanocomposite dispersions: processes, compositions, and uses thereof |
| CN103173161A (en) * | 2013-03-08 | 2013-06-26 | 东莞新能源科技有限公司 | Preparation method of lithium ion battery cathode sheet adhesive emulsion |
| JP2014203805A (en) * | 2013-04-10 | 2014-10-27 | 日本ゼオン株式会社 | Particulate binder for lithium ion secondary battery negative electrode, slurry composition for lithium ion secondary battery negative electrode, and lithium ion secondary battery |
| WO2015160794A1 (en) * | 2014-04-14 | 2015-10-22 | Ecosynthetix Ltd. | Bio-based nanoparticle and composite materials derived therefrom |
| KR101698745B1 (en) * | 2015-08-03 | 2017-01-23 | 주식회사 한솔케미칼 | Core-shell structured binders for use of anode materials of lithium ion secondary battery and method for preparing using the same, and slurry comprising said binders |
| WO2017056466A1 (en) * | 2015-09-28 | 2017-04-06 | 日本ゼオン株式会社 | Binder composition for nonaqueous secondary battery electrodes, slurry composition for nonaqueous secondary battery electrodes, electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN108929401A (en) * | 2018-06-25 | 2018-12-04 | 重庆云天化瀚恩新材料开发有限公司 | A kind of lithium battery silicium cathode adhesive and preparation method thereof |
| CN113228397A (en) * | 2018-12-28 | 2021-08-06 | 三星Sdi株式会社 | Separator for lithium secondary battery and lithium secondary battery including the same |
| CN114520329A (en) * | 2020-11-19 | 2022-05-20 | 比亚迪股份有限公司 | Adhesive, preparation method thereof and slurry |
| KR20220087853A (en) * | 2020-12-18 | 2022-06-27 | 주식회사 엘지화학 | Electrode binder composition for rechargeable battery and electrode mixture including the same |
| CN113555558A (en) * | 2021-07-12 | 2021-10-26 | 珠海冠宇电池股份有限公司 | Emulsion type binder and lithium ion battery comprising same |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of core-shell latex particles by emulsion co-polymerization of styrene and butyl acrylate, and evaluation of their pigment properties in emulsion paints;Borthakur, LJ ; Jana, T;《JOURNAL OF COATINGS TECHNOLOGY AND RESEARCH》;第7卷(第6期);第765-772页 * |
| 核壳型聚丙烯酰胺类聚合物的合成与性能研究;史冬敏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 (月刊)》(第10期);B016-311 * |
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| WO2024002199A1 (en) | 2024-01-04 |
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