CN117143545A - Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device - Google Patents
Adhesive and preparation method thereof, negative electrode plate, battery and power utilization device Download PDFInfo
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- CN117143545A CN117143545A CN202311423953.4A CN202311423953A CN117143545A CN 117143545 A CN117143545 A CN 117143545A CN 202311423953 A CN202311423953 A CN 202311423953A CN 117143545 A CN117143545 A CN 117143545A
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012804 iterative process Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides an adhesive, a preparation method thereof, a negative electrode plate, a battery and an electric device. The binder comprises a polymer comprising structural units of formula (I) and formula (II) and formula (III), and at least one selected from structural units of formula (IV), formula (V) or formula (VI); r1, R2, R4, R6, R7 are each independently selected from H, unsubstituted or substituted C 1 ‑C 20 Alkyl, unsubstituted or substituted C 1 ‑C 20 At least one of alkoxy groups; and R3, R5 are each independently selected from unsubstituted or substituted C 1 ‑C 20 At least one of alkyl groups; substituted C 1 ‑C 20 Alkyl and substituted C 1 ‑C 20 The substituents in the alkoxy groups are each independently selected from at least one of hydroxy, halogen or amino. The adhesive is used for solving the problems of cracking of the pole piece during thick coating, battery performance degradation caused by the cracking of the pole piece, and the like.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to an adhesive and a preparation method thereof, a negative pole piece, a battery and an electric device.
Background
In recent years, the rapid development of the new energy automobile industry and the energy storage industry drives the rapid development of lithium batteries. The battery energy density is an indispensable key index in the iterative process of the lithium battery technology. In the prior researches, the improvement of the energy density of the battery is mainly focused on the research and development of main material graphite and the improvement of the working voltage of the battery; or by thick coating of the pole piece, high loading is achieved.
However, in preparing a pole piece coating, the thicker the coating, the higher the density, the greater the internal stress, resulting in a coating with a greater elastic modulus. In this case, the stress accumulation cannot be uniformly released, resulting in cracking of the pole piece.
Therefore, how to improve the flexibility of the pole piece, so that the pole piece is not cracked when thick coated, and further, the improvement of the battery performance becomes a problem to be solved in the field.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to provide a binder and a method for producing the same, which solve the problems associated with the cracking of a pole piece during thick coating and the deterioration of battery performance caused by the cracking. The application also provides a negative electrode plate, a battery comprising the negative electrode plate and an electric device comprising the battery.
In order to achieve the above object, a first aspect of the present application provides an adhesive comprising a polymer comprising a structural unit represented by formula (I) and a structural unit represented by formula (II) and a structural unit represented by formula (III), and at least one selected from a structural unit represented by formula (IV), a structural unit represented by formula (V) or a structural unit represented by formula (VI);
，/>，/>，
、/>、/>；
Wherein R1, R2, R4, R6, R7 are each independently selected from H, unsubstituted or substituted C 1 -C 20 Alkyl, unsubstituted or substituted C 1 -C 20 At least one of alkoxy groups, wherein the substituted C 1 -C 20 Substituent groups in alkyl groups and said substituted C 1 -C 20 The substituent groups in the alkoxy groups are respectively and independently selected from at least one of hydroxyl, halogen or amino;
r3 and R5 are each independently selected from unsubstituted or substituted C 1 -C 20 At least one of alkyl groups, said substituted C 1 -C 20 The substituent group in the alkyl group is selected from at least one of hydroxyl, halogen or amino.
In the embodiment of the application, the adhesive has enhanced adhesion by the combined action of the structural unit represented by the formula (I) and the structural unit represented by the formula (II) and the structural unit represented by the formula (III), and at least one selected from the structural unit represented by the formula (IV), the structural unit represented by the formula (V) and the structural unit represented by the formula (VI), so that stress accumulation in the pole piece can be reduced or eliminated, the flexibility of the pole piece can be improved, the pole piece is not cracked in thick coating, and the single-sided coating quality of the negative electrode slurry in unit area on the pole piece can be improved.
In any embodiment, R1, R2, R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of alkyl groups;
and/or R3 is selected from unsubstituted C 1 -C 4 At least one of alkyl groups;
and/or R5 is selected from unsubstituted or substitutedC 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group.
The adhesive in the embodiments has further enhanced adhesive force, can further reduce or eliminate stress accumulation in the pole piece, improves the flexibility of the pole piece, and ensures that the pole piece is not cracked when thick coated.
In any embodiment, the polymer comprises at least one structural unit represented by formula (IV), wherein R4 is selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group. The acrylate group in the structural unit represented by the formula (IV) is beneficial to enhancing the cohesive force of the adhesive and increasing the wettability of the electrolyte to the pole piece.
In any embodiment, the polymer comprises at least one structural unit represented by formula (IV) and at least one structural unit represented by formula (V), wherein R4, R6 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group. The ester group in the structural unit represented by the formula (IV) is beneficial to enhancing the cohesive force of the adhesive and increasing the wettability of the electrolyte to the pole piece. The amide group in the structural unit represented by formula (V) is advantageous in enhancing the cohesive force of the adhesive.
In any embodiment, the polymer comprises at least one structural unit represented by formula (IV), at least one structural unit represented by formula (V), and at least one structural unit represented by formula (VI), wherein R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group. The ester group in the structural unit represented by the formula (IV) is beneficial to enhancing the cohesive force of the adhesive and increasing the wettability of the electrolyte to the pole piece. The amide group in the structural unit represented by formula (V) and the cyano group in the structural unit represented by formula (VI) are advantageous in enhancing the adhesion of the adhesive.
In any embodiment, in the polymer, the weight percentage of the structural unit represented by formula (I) is 4.5% to 8%, the weight percentage of the structural unit represented by formula (II) is 12% to 21%, the weight percentage of the structural unit represented by formula (III) is 3% to 6.5%, and the weight percentage of at least one selected from the structural unit represented by formula (IV), the structural unit represented by formula (V) or the structural unit represented by formula (VI) is 68% to 77%. By making the mass percentage of each structural unit within the above range, it is advantageous to further enhance the cohesive force of the adhesive.
In any embodiment, the glass transition temperature of the polymer is-15 to 15 ℃. By making the glass transition temperature of the polymer within the above range, the adhesive is favorable to have proper flexibility, and further, the pole piece is favorable to have proper flexibility, so that the pole piece is not cracked when thick coated.
In any embodiment, the weight average molecular weight of the polymer is 40 to 100 tens of thousands. By making the weight average molecular weight of the polymer within the above range, it is advantageous to give the binder fluidity suitable for practical production needs.
A second aspect of the application provides a method of preparing a binder as described hereinabove, the method comprising:
Adding a monomer corresponding to a structural unit represented by the formula (I) and a monomer corresponding to a structural unit represented by the formula (II) into a solvent, and reacting in the presence of a first surfactant and a first initiator to prepare a first emulsion;
adding a monomer corresponding to a structural unit represented by formula (III) and at least one monomer selected from a monomer corresponding to a structural unit represented by formula (IV), a monomer corresponding to a structural unit represented by formula (V) or a monomer corresponding to a structural unit represented by formula (VI) into a first emulsion, and reacting in the presence of a second surfactant to prepare a second emulsion;
and heating the second emulsion, and reacting in the presence of a second initiator to obtain the adhesive.
The adhesive is prepared by polymerizing the monomer corresponding to the structural unit serving as a monomer raw material, the obtained adhesive has enhanced adhesive force, stress accumulation in the pole piece can be reduced or eliminated, the flexibility of the pole piece is improved, the pole piece is not cracked during thick coating, and the single-sided coating quality of the negative electrode slurry in unit area on the pole piece is improved.
The third aspect of the application provides a negative electrode tab comprising a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises the binder of the first aspect of the application or the binder prepared by the method of the second aspect of the application. By including the binder described above, the flexibility of the pole piece is improved so that the pole piece does not crack when thick coated.
In any embodiment, the mass percentage of the binder is 1.2% -2.2% based on the total mass of the negative electrode film layer. The mass percentage of the binder is in the range, so that the flexibility of the pole piece is improved, the pole piece is not cracked in thick coating, and the content of the active material in the negative electrode film layer is not reduced.
In any embodiment, the negative electrode film layer further comprises a stabilizer, wherein the stabilizer comprises at least one of sodium carboxymethyl cellulose, sodium alginate or cyclodextrin sodium. By including the stabilizer, dispersion of the anode active material in the anode film layer is facilitated.
A fourth aspect of the application provides a battery comprising the negative electrode tab of the third aspect of the application. The battery has an increased battery energy density.
A fifth aspect of the application provides an electrical device comprising a battery of the fourth aspect of the application. The power utilization device is provided with a durable power supply.
The present application provides an adhesive comprising a polymer comprising a structural unit represented by formula (I) and a structural unit represented by formula (II) and a structural unit represented by formula (III), and at least one selected from a structural unit represented by formula (IV), a structural unit represented by formula (V) or a structural unit represented by formula (VI). Through the combined action of the structural units, the adhesive has enhanced adhesive force, can reduce or eliminate stress accumulation in the pole piece, improves the flexibility of the pole piece, ensures that the pole piece is not cracked when thick coated, and increases the single-sided coating quality of the negative electrode slurry in unit area on the pole piece. Therefore, for the battery prepared by using the binder, the direct current impedance of the battery can be reduced, and the energy density, the cycle performance and the storage performance of the battery can be improved.
The application also provides a method for preparing the adhesive. In the method, at least one monomer selected from a monomer corresponding to a structural unit represented by a formula (I), a monomer corresponding to a structural unit represented by a formula (II), a monomer corresponding to a structural unit represented by a formula (III), a monomer corresponding to a structural unit represented by a formula (IV), a monomer corresponding to a structural unit represented by a formula (V) or a monomer corresponding to a structural unit represented by a formula (VI) is used as a monomer raw material to prepare the adhesive, so that the obtained adhesive has enhanced adhesive force, can reduce or eliminate stress accumulation in the pole piece, improve the flexibility of the pole piece, prevent the pole piece from cracking during thick coating, and increase the single-sided coating quality of the negative electrode slurry in a unit area on the pole piece. Therefore, for the battery prepared by using the binder, the direct current impedance of the battery can be reduced, and the energy density, the cycle performance and the storage performance of the battery can be improved.
Drawings
FIG. 1 is a schematic diagram of a crosslinked network of a binder according to one embodiment of the present application;
fig. 2 shows a schematic diagram of the hydrogen bonding of an adhesive according to an embodiment of the present application. Wherein strong hydrogen bonds with large bond energy are formed between the exemplary stabilizers CMC-Na themselves are shown in the upper part of fig. 2; in the lower left part of fig. 2, reversible hydrogen bonds are shown between the binder of an embodiment of the application and the exemplary stabilizer CMC-Na; the right lower part of fig. 2 shows that the polar groups of the binder according to an embodiment of the present application form hydrogen bonds with each other in both strength and weakness;
Fig. 3 is a schematic view of a battery cell according to an embodiment of the present application;
fig. 4 is an exploded view of a battery cell according to an embodiment of the present application shown in fig. 3;
fig. 5 is a schematic view of a battery module according to an embodiment of the present application;
fig. 6 is a schematic view of a battery pack according to an embodiment of the present application;
fig. 7 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 6;
fig. 8 is a schematic view of an electric device in which a battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5, a battery cell; 51 a housing; 52 electrode assembly; 53 top cap assembly.
Detailed Description
Hereinafter, embodiments of the binder, the method for preparing the same, the negative electrode tab, the battery, and the electric device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the figures and the following description are provided for a thorough understanding of the present application by those skilled in the art, and are not intended to limit the claimed subject matter of the present application.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
In the related art, in order to increase the energy density of the battery, one means that may be adopted is to thick coat an active material coating on the electrode sheet to achieve a high load amount, thereby increasing the amount of active material per unit area of the negative electrode sheet. However, when preparing an active material coating, the thicker the coating, the higher the density, the greater the internal stress, resulting in a coating with a greater elastic modulus, and a stress build-up that is not uniformly releasable, resulting in a crack in the pole piece. When the coating thickness of the pole piece is increased, the evaporation of water in the pole piece drying process can also cause local accumulation and release of the internal stress of the pole piece, and the pole piece is easy to crack, so that the pole piece has low quality and low rate, and the assembled battery cell also has lithium precipitation risk.
Aiming at the problems, the prior solution is to add a plasticizer to improve the flexibility of the pole piece in the process of preparing the negative electrode slurry. However, this method has some disadvantages and risks, such as the need for additional addition of a delivery pipe; excessive addition can deteriorate the electrical performance of the cell; in the high-speed thick coating process, part of the plasticizer has strong hydrophilicity, the residual quantity of small plasticizer molecules in the pole piece is high, the performance of the battery cell can be deteriorated, and meanwhile, the dryness of the pole piece can not be ensured; the addition of the plasticizer also reduces the content of the anode active material in the anode slurry.
Based on the above, the application provides an adhesive and a preparation method thereof, a negative electrode plate, a battery and an electric device. The present application and alternative embodiments are described in more detail below.
Adhesive agent
The present application provides an adhesive comprising a polymer comprising a structural unit represented by formula (I) and a structural unit represented by formula (II) and a structural unit represented by formula (III), and at least one selected from a structural unit represented by formula (IV), a structural unit represented by formula (V) or a structural unit represented by formula (VI);
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wherein R1, R2, R4, R6, R7 are each independently selected from H, unsubstituted or substituted C 1 -C 20 Alkyl, unsubstituted or substituted C 1 -C 20 At least one of alkoxy groups, wherein, substituted C 1 -C 20 Substituent groups in alkyl groups and substituted C 1 -C 20 The substituent groups in the alkoxy groups are each independently selected from at least one of hydroxyl, halogen or amino.
R3 and R5 are each independently selected from unsubstituted or substituted C 1 -C 20 At least one of alkyl groups, substituted C 1 -C 20 The substituent group in the alkyl group is selected from at least one of hydroxyl, halogen or amino.
“C 1 -C 20 Alkyl "refers to a straight or branched chain aliphatic hydrocarbon group having 1 to 20 carbon atoms. Alternative C 1 -C 20 Alkyl includes straight or branched C having 1 to 10 carbon atoms 1 -C 10 An alkyl group. Alternative C 1 -C 20 Alkyl includes straight or branched C having 1 to 8 carbon atoms 1 -C 8 An alkyl group. Alternative C 1 -C 20 Alkyl includes straight or branched C having 1 to 6 carbon atoms 1 -C 6 An alkyl group. Alternative C 1 -C 20 Alkyl includes straight or branched C having 1 to 4 carbon atoms 1 -C 4 An alkyl group. Alternative C 1 -C 20 Alkyl groups include C having 1 to 2 carbon atoms 1 -C 2 An alkyl group. C (C) 1 -C 20 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl.
“C 1 -C 20 Alkoxy "means" C 1 -C 20 Alkyloxy ", wherein" C 1 -C 20 Alkyl "moieties are described above as" C 1 -C 20 Alkyl "is as defined. Alternative C 1 -C 20 Alkoxy includes C 1 -C 10 An alkoxy group. Alternative C 1 -C 20 Alkoxy includes C 1 -C 8 An alkoxy group. Alternative C 1 -C 20 Alkoxy includes C 1 -C 6 An alkoxy group. Alternative C 1 -C 20 Alkoxy includes C 1 -C 4 An alkoxy group. Alternative C 1 -C 20 Alkoxy includes C 1 -C 2 An alkoxy group. C (C) 1 -C 20 Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decyloxy.
The "structural unit represented by the formula (I)" may include one or more structural units represented by the formula (I). For example, the binder in an embodiment of the present application may include a structural unit represented by formula (I) in which R1 is H; or the binder in the embodiment of the present application may include a structural unit represented by formula (I) in which R1 is H and R1 is methyl at the same time. The meanings of the expressions "structural unit represented by formula (II)", "structural unit represented by formula (III)", "structural unit represented by formula (IV)", "structural unit represented by formula (V) and" structural unit represented by formula (VI) "are explained identically.
By "unsubstituted" is meant that the recited group has no substituent groups.
"substituted" means that the recited group has a substituent. Examples of such substituents include, but are not limited to, hydroxy (OH), halogen (F, cl, br, I), amino (NH) 2 ) Cyano (CN), nitro (NO 2 ）、C 1 -C 10 Alkylamino, phenyl (Ph). When a group is substituted, it may have more than 1 substituent group, for example, 1, 2 or 3 substituent groups. For example, a substituted group may have 1 or 2 substituent groups.
The present application has found that the principal stress of pole piece cracking results from the strong hydrogen bonding formed between stabilizers such as sodium carboxymethyl cellulose (CMC-Na). The side chain of the binder in the embodiment of the application comprises at least one polar group of carboxyl, ester, amido and cyano. Although the mechanism is not yet clear, in the process of coating the anode slurry including the binder of the embodiment of the present application on the anode current collector, the binder itself undergoes thermal crosslinking to form a uniform network as schematically shown in fig. 1, while more contact sites can be provided on the surface of the active material. The polar groups of these contact sites are capable of forming reversible hydrogen bonds of different bond energies with the hydroxyl, carboxyl groups of stabilizers such as CMC-Na (fig. 2), greatly reducing the likelihood of strong hydrogen bonds of large bond energies, non-rotatable (fig. 2) between stabilizers such as CMC-Na. Meanwhile, the polar groups on the side chains of the binder form hydrogen bonds with different bond energies together with each other (figure 2). In the process of pole piece drying, weak hydrogen bonds with low bond energy can be broken due to local accumulation of drying stress, healing is achieved after stress release, and strong hydrogen bonds with high bond energy are not easy to break, so that the integral structure of the pole piece is maintained.
The structural unit represented by formula (I) is derived from a rigid monomer, and can keep a good space expansion structure of the adhesive, so that excessive deformation of a molecular chain during the drying process of the pole piece can not happen to adversely affect cohesive force. The cohesive force of the adhesive and thus the cohesive force of the pole piece can be enhanced by including the structural unit represented by formula (I).
The structural unit represented by formula (II) includes a carboxyl group. The structural unit represented by formula (IV), the structural unit represented by formula (V), or the structural unit represented by formula (VI) includes an ester group, an amide group, and a cyano group, respectively. The polar groups included in these structural units are capable of forming reversible hydrogen bonds with the stabilizer in the slurry or hydrogen bonds with different bond energies from each other. These hydrogen bonds facilitate uniform release of the stress build-up of the pole piece during the pole piece drying process.
In addition, in the pole piece drying process, siloxane in the structural unit represented by the formula (III) is hydrolyzed and condensed to generate Si-O-Si bonds, so that on one hand, the linear structure is crosslinked into a body type structure, and on the other hand, the Si-O bonds can rotate by 360 degrees, and the stress accumulation in the pole piece drying process is reduced.
Thus, the adhesive in the embodiment of the application has enhanced adhesive force through the combined action of the structural unit represented by the formula (I) and the structural unit represented by the formula (II) and the structural unit represented by the formula (III), and at least one selected from the structural unit represented by the formula (IV), the structural unit represented by the formula (V) and the structural unit represented by the formula (VI), can reduce or eliminate stress accumulation in the pole piece, improve the flexibility of the pole piece, prevent the pole piece from cracking during thick coating, and increase the single-sided coating quality of the negative electrode slurry in unit area on the pole piece.
In some embodiments, R1, R2, R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups. For example, R1, R2, R4, R6, R7 are each independently selected from at least one of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.
In some embodiments, R3 is selected from unsubstituted C 1 -C 4 At least one of the alkyl groups. For example, R3 is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.
In some embodiments, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of the alkyl groups. Where substituted C 1 -C 8 Substituents in the alkyl group include, but are not limited to, hydroxyl groups. Alternatively, R5 is selected from unsubstituted C 1 -C 8 At least one of the alkyl groups. For example, R5 is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, hexyl, heptyl, octyl, and isooctyl. Alternatively, R5 is selected from hydroxy-substituted C 1 -C 8 At least one of the alkyl groups. For example, R5 is selected from at least one of hydroxy-substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, hexyl, heptyl, octyl, isooctyl.
The adhesive in the embodiments has further enhanced adhesive force, can further reduce or eliminate stress accumulation in the pole piece, improves the flexibility of the pole piece, and ensures that the pole piece is not cracked when thick coated.
In some embodiments, the polymer comprises at least one structural unit represented by formula (IV), wherein R4 is selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 Substituents in the alkyl group include, but are not limited to, hydroxy. Examples of R4 and R5 are as described above and are not described in detail herein.
"the polymer includes at least one structural unit represented by the formula (IV)" means that more than one structural unit represented by the formula (IV) may be included in the polymer. For example, the polymer may also include R4 as H and R5 as isooctyl; r4 is H, R5 is ethyl; r4 is H, R5 is butyl; r4 is methyl, R5 is methyl; and R4 is H, R5 is a structural unit of hydroxy-substituted ethyl group represented by formula (IV), but is not limited thereto.
Although the mechanism is not yet clear, the acrylate groups in the binders in these embodiments increase the wettability of the electrolyte to the pole piece.
In some embodiments, the polymer comprises at least one structural unit represented by formula (IV) and at least one structural unit represented by formula (V), wherein R4, R6 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 Substituents in the alkyl group include, but are not limited to, hydroxy. Examples of R4, R6 and R5 are as described above and are not described in detail herein.
Although the mechanism is not yet clear, the acrylate groups in the binders in these embodiments increase the wettability of the electrolyte to the pole piece. In addition, polar groups such as amide groups are added in the side chains, so that the cohesive force of the adhesive is enhanced.
In some embodiments, the polymer comprises at least one structural unit represented by formula (IV), at least one junction represented by formula (V)Building block and at least one structural unit represented by formula (VI), wherein R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 Substituents in the alkyl group include, but are not limited to, hydroxyl groups. Examples of R4, R6, R7 and R5 are as described above and are not described in detail herein.
Although the mechanism is not yet clear, in these embodiments the structural unit side chain of the binder includes at least one polar group of a carboxyl group, an amide group, a cyano group, and an ester group. These polar groups form reversible hydrogen bonds of different bond energies with stabilizers such as CMC-Na. In the pole piece drying process, weak hydrogen bonds can be broken due to local accumulation of drying stress, healing is achieved after stress release, and the strong hydrogen bonds are not easy to break, so that the integral structure of the pole piece is maintained.
In some embodiments, in the polymer, the mass percent of structural units represented by formula (I) is 4.5% -8%, alternatively 5% -7.5%, alternatively 5.5% -7.0%, alternatively 6.0% -6.5%; the mass percentage of the structural unit represented by the formula (II) is 12% -21%, optionally 14% -20%, optionally 15% -19%, optionally 16% -18%; the mass percentage of the structural unit represented by the formula (III) is 3% -6.5%, optionally 3.5% -6%, optionally 4% -5%; and 68 to 77% by mass, optionally 69 to 76% by mass, optionally 70 to 75% by mass, optionally 71 to 74% by mass of at least one selected from the structural unit represented by formula (IV), the structural unit represented by formula (V) and the structural unit represented by formula (VI).
Although the mechanism is not yet clarified, controlling the mass percentage of at least one selected from the structural unit represented by the formula (I), the structural unit represented by the formula (II), the structural unit represented by the formula (III), and the structural unit represented by the formula (IV), the structural unit represented by the formula (V), or the structural unit represented by the formula (VI) within the above-mentioned range is advantageous in that the glass transition temperature of the polymer is within a proper range and the binder molecular chain maintains a certain space mobility during the pole piece drying process, thereby uniformly releasing the stress accumulation due to the evaporation of moisture during the drying process. The appropriate amount of silane chain is advantageous in controlling the degree of crosslinking to be kept within a desired level. The structural unit represented by formula (I) is derived from a rigid monomer, and the inclusion of an appropriate amount of the structural unit represented by formula (I) is advantageous in improving the cohesive force of the adhesive.
In some embodiments, the glass transition temperature of the polymer is-15 to 15 ℃, alternatively-14 to 10 ℃, alternatively-13 to 8 ℃, alternatively-11 to 6 ℃, alternatively-9~4 ℃, alternatively-7~2 ℃, alternatively-5~0 ℃.
Although the mechanism is not yet clear, the glass transition temperature Tg of the polymer reflects the flexibility of the binder, affecting to some extent the flexibility of the pole piece. The pole piece with certain flexibility is an ideal pole piece. The pole piece is too soft, so that the cohesive force is insufficient, the pole piece is large in rebound, the pole piece is too hard, and the pole piece is easy to crack. The glass transition temperature of the polymer is controlled in the range, so that the adhesive is favorable to have proper flexibility, the pole piece is further favorable to have proper flexibility, the pole piece is not cracked during thick coating, and the single-sided coating quality of the negative electrode slurry in unit area on the pole piece is improved.
In some embodiments, the weight average molecular weight of the polymer is 40 to 100, alternatively 45 to 90, alternatively 45 to 80, alternatively 45 to 70, alternatively 45 to 60.
Although the mechanism is not clear, controlling the weight average molecular weight of the polymer within the above-mentioned range is advantageous in that the binder has fluidity suitable for practical production.
Method for preparing adhesive
The application also provides a preparation method of the adhesive. The method comprises the following steps.
The monomer corresponding to the structural unit represented by the formula (I) and the monomer corresponding to the structural unit represented by the formula (II) are added into a solvent, and reacted in the presence of a first surfactant and a first initiator to prepare a first emulsion.
And adding at least one monomer selected from the group consisting of a monomer corresponding to the structural unit represented by formula (III), a monomer corresponding to the structural unit represented by formula (IV), a monomer corresponding to the structural unit represented by formula (V) and a monomer corresponding to the structural unit represented by formula (VI) to the first emulsion, and reacting in the presence of a second surfactant to prepare a second emulsion.
The second emulsion is heated and reacted in the presence of a second initiator to produce the adhesive of the application.
In some embodiments, solvents commonly used in the art may be used. For example, the solvent may include deionized water, but is not limited thereto.
In some embodiments, the first surfactant and the second surfactant may be the same or different, and surfactants commonly used in the art may be used. For example, the surfactant may include at least one of ammonium polyoxyethylene nonylphenol ether sulfate, polyoxyethylene lauryl alcohol ether, but is not limited thereto.
In some embodiments, the first initiator and the second initiator may be the same or different, and initiators commonly used in the art may be used. For example, the initiator may include at least one of ammonium persulfate, potassium persulfate, sodium persulfate, dibenzoyl peroxide, hydrogen peroxide/diabolo, t-butyl hydroperoxide/diabolo, but is not limited thereto. Alternatively, the first initiator may comprise ammonium persulfate. Alternatively, the second initiator may comprise at least one of ammonium persulfate or t-butyl hydroperoxide/diabolo.
In some embodiments, the second emulsion may be heated to 70-100 ℃. Optionally, the second emulsion may be heated to 80-90 ℃, but is not limited thereto.
Although the mechanism is not clear, in this method, at least one monomer selected from the group consisting of a monomer corresponding to a structural unit represented by formula (I), a monomer corresponding to a structural unit represented by formula (II), a monomer corresponding to a structural unit represented by formula (III), and a monomer corresponding to a structural unit represented by formula (IV), a monomer corresponding to a structural unit represented by formula (V), and a monomer corresponding to a structural unit represented by formula (VI) is used as a monomer raw material for polymerization to prepare an adhesive, and the obtained adhesive has enhanced adhesion, can reduce or eliminate stress accumulation in a pole piece, improve flexibility of the pole piece, prevent the pole piece from cracking at the time of thick coating, and increase single-sided coating quality of a negative electrode slurry per unit area on the pole piece. Therefore, for the battery prepared by using the binder, the direct current impedance of the battery can be reduced, and the energy density, the cycle performance and the storage performance of the battery can be improved.
Regarding the reaction conditions such as the reaction temperature, the reaction time, the reaction pressure, the addition amount of the reagent, and other optional reagents (e.g., molecular weight regulator, pH regulator, etc.), and the addition amount thereof in the above-mentioned method, those skilled in the art can select and adjust the reaction conditions according to actual needs, and will not be described herein.
Negative electrode slurry composition
The application also provides a negative electrode slurry composition. The negative electrode slurry composition includes a negative electrode active material, the binder described above, and a stabilizer. The binder mainly plays a role in binding between the anode active materials and the base material. The stabilizer mainly plays a role in suspending during the stirring of the cathode slurry, so that the active material such as graphite does not settle during the stirring.
In some embodiments, the binder may be 1.2% -2.2%, alternatively 1.4% -2.0%, alternatively 1.6% -1.8% by mass relative to the total solids content of the negative electrode slurry composition.
In some embodiments, the stabilizer may be 0.5% to 1.2%, alternatively 0.6% to 1.1%, alternatively 0.8% to 1.0% by mass relative to the total solids content of the negative electrode slurry composition.
In some embodiments, the stabilizer is selected from the group consisting of hydroxyl, carboxyl, and the like groups capable of forming hydrogen bonds. For example, the stabilizer may include, but is not limited to, sodium carboxymethyl cellulose, sodium alginate, sodium cyclodextrin. Alternatively, the stabilizer may include, but is not limited to, sodium carboxymethyl cellulose, sodium alginate, sodium hydroxypropyl cyclodextrin, sodium carboxymethyl cyclodextrin, sodium hyperbranched cyclodextrin, sodium sulfobutyl-beta cyclodextrin, and the like.
The polar groups in the adhesive in the embodiment of the application form hydrogen bonds with different bond energies with hydroxyl groups, carboxyl groups and other groups capable of forming hydrogen bonds in the stabilizers, so that the possibility of forming hydrogen bonds between the stabilizers is greatly reduced. In the process of pole piece drying, weak hydrogen bonds with low bond energy can be broken due to local accumulation of drying stress, healing is achieved after stress release, and strong hydrogen bonds with high bond energy are not easy to break, so that the integral structure of the pole piece is maintained. Therefore, the pole piece is not cracked in thick coating, and the single-sided coating quality of the negative electrode slurry in unit area on the pole piece is improved.
Negative pole piece
The application also provides a negative pole piece. The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector. The negative electrode film layer includes the binder described above, or a binder prepared by the method described above.
In some embodiments, the binder may be 1.2% -2.2%, optionally 1.4% -2.0%, optionally 1.6% -1.8% by mass of the total mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer further includes a stabilizer. The stabilizer is selected from substances including hydroxyl, carboxyl, etc. groups capable of forming hydrogen bonds. For example, the stabilizers include, but are not limited to, sodium carboxymethyl cellulose, sodium alginate, sodium cyclodextrin. Alternatively, the stabilizer includes, but is not limited to, sodium carboxymethyl cellulose, sodium alginate, sodium hydroxypropyl cyclodextrin, sodium carboxymethyl cyclodextrin, sodium hyperbranched cyclodextrin, sodium sulfobutyl-beta cyclodextrin, and the like.
In some embodiments, the stabilizer may be 0.5% -1.2%, optionally 0.6% -1.1%, optionally 0.8% -1.0% by mass of the total mass of the negative electrode film layer.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, or the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, or silicon alloys. The tin-based material may be selected from at least one of elemental tin, a tin oxide, or a tin alloy. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer may also optionally include other binders. The binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), or carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent may be at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene or carbon nanofibers.
In some embodiments, the negative electrode film layer may also optionally include other adjuvants, such as thickening agents.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
The battery and the power consumption device according to the present application will be described below with reference to the drawings.
In one embodiment of the present application, a battery is provided. The battery comprises a binder selected from the group consisting of the binders described hereinabove, binders prepared by the methods described hereinabove, or the negative electrode tabs described hereinabove.
The term "battery" referred to herein refers to a battery cell, a battery module, or a battery pack. The following description will be given separately.
Typically, the battery cell includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
Positive electrode plate
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer comprises a positive active material.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, when the battery cell is a lithium ion battery, the positive electrode active material may be a positive electrode active material for a lithium ion battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/ 3 Mn 1/3 O 2 (also referred to as NCM) 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM) 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM) 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM) 622 ）、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM) 811 ) Lithium nickel cobalt aluminum oxide (e.g. LiNi 0.85 Co 0.15 Al 0.05 O 2 ) And at least one of its modified compounds and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO 4 (also abbreviated as LFP)), composite material of lithium iron phosphate and carbon, and manganese lithium phosphate (such as LiMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, and a composite material of lithium manganese phosphate and carbon.
The battery is charged and discharged with the release and consumption of Li, and the molar contents of Li are different when the battery is discharged to different states. In the application, the molar content of Li is the initial state of the material, namely the state before charging, and the molar content of Li can be changed after charge and discharge cycles when the positive electrode material is applied to a battery system.
In the application, in the list of the positive electrode materials, the molar content of O is only a theoretical state value, the molar content of oxygen can be changed due to the oxygen release of the crystal lattice, and the actual molar content of O can be floated.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
Negative pole piece
The negative electrode sheet is as described above and will not be described in detail herein.
Electrolyte composition
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
Isolation film
In some embodiments, a separator is also included in the battery cell. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the battery cell may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the exterior packaging of the battery cell may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The outer package of the battery cell may also be a pouch, such as a pouch-type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the battery cell is not particularly limited in the present application, and may be cylindrical, square or any other shape. For example, fig. 3 is a square-structured battery cell 5 as one example.
In some embodiments, referring to fig. 4, the overpack may include a housing 51 and a cap assembly 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodating chamber, and the top cover assembly 53 can be provided to cover the opening to close the accommodating chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of the electrode assemblies 52 included in the battery cell 5 may be one or more, and those skilled in the art may select the number according to specific practical requirements.
In some embodiments, the battery cells may be assembled into a battery module, and the number of battery cells included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Fig. 5 is a battery module 4 as an example. Referring to fig. 5, in the battery module 4, a plurality of battery cells 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of battery cells 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a housing having an accommodating space in which the plurality of battery cells 5 are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 6 and 7 are battery packs 1 as an example. Referring to fig. 6 and 7, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device, which comprises the battery provided by the application. The battery may be used as a power source for the power device and may also be used as an energy storage unit for the power device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a battery cell, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 8 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. To meet the high power and high energy density requirements of the power device for the battery, a battery pack or battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a battery cell can be used as a power supply.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Preparation of the adhesive
Example 1
1.1 18 parts of deionized water, 0.06 part of dodecyl mercaptan and 0.4 part of ammonium nonylphenol polyoxyethylene ether sulfate are mixed in a reaction kettle according to parts by weight, and heated to 60 ℃. Then, 1.2 parts of styrene and 3 parts of acrylic acid were added, and after the completion of the dropwise addition, the pH was adjusted to about 7 with sodium hydrogencarbonate. Then the temperature is raised to 75 ℃, 0.2 part of initiator ammonium persulfate is added for reaction for 1h. And then cooling to 40 ℃ to obtain the first emulsion.
1.2 The first emulsion was added with 20 parts by weight of deionized water, 0.09 part by weight of dodecyl mercaptan, and 0.18 part by weight of polyoxyethylene lauryl ether. Then, the mixture was heated to 60℃and stirred for 0.5 hour, and 3.3 parts of isooctyl acrylate (2-EHA), 2 parts of Ethyl Acrylate (EA), 1.8 parts of Butyl Acrylate (BA), 4.1 parts of methyl methacrylate, 2.6 parts of hydroxyethyl acrylate and 0.9 part of vinyltriethoxysilane were added thereto and stirred for 1 hour. After fully stirring, cooling to 40 ℃, then adding 0.2 part of ammonium polyoxyethylene nonylphenol sulfate, and uniformly stirring to obtain a second emulsion.
1.3 And heating, stirring and heating the second emulsion to 80-90 ℃, keeping the temperature at 80-90 ℃, dropwise adding 0.2 part of ammonium persulfate solution, and reacting for 2.5 hours after the dropwise adding is finished. Then, the reaction mixture was cooled to 50℃and 0.12 part of rongalite and 0.08 part of t-butyl hydroperoxide were added thereto, followed by thermal insulation for 2 hours. Then cooled, the pH was adjusted to about 7 with sodium bicarbonate, and discharged to obtain a binder emulsion.
Example 2 to example 14
The same preparation as in example 1 was used, except that the kind of monomer added and the amount added were different. The specific types of monomers added, amounts, molecular weights of the polymers obtained and glass transition temperatures are shown in Table 1 below.
Example 2 differs from example 1 in that vinyltrimethoxysilane was used instead of vinyltriethoxysilane in example 1.
Example 3 differs from example 1 in that the ester monomers used in example 1, isooctyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and hydroxyethyl acrylate, were replaced with methyl methacrylate.
Example 4 differs from example 1 in that the ester monomers used in example 1, isooctyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and hydroxyethyl acrylate, were replaced with isooctyl acrylate.
Examples 5 to 12 differ from example 1 in the amount of each type of monomer added.
Example 13 differs from example 1 in that an acrylamide monomer was further added in step 1.2, specifically, 0.2 parts by weight of the acrylamide monomer was used in place of 0.1 parts by weight of isooctyl acrylate and 0.1 parts by weight of butyl acrylate in example 1.
Example 14 differs from example 1 in that acrylamide and acrylonitrile monomers, specifically 0.2 parts by weight of acrylamide monomer and 0.1 parts by weight of acrylonitrile were further added in step 1.2 instead of 0.1 parts by weight of isooctyl acrylate, 0.1 parts by weight of butyl acrylate and 0.1 parts by weight of methyl methacrylate in example 1.
Comparative example 1
The binder used in comparative example 1 was the binder polyacrylic acid (PAA, weight average molecular weight 70 ten thousand, glass transition temperature 50 ℃) commonly used in the art.
Weight average molecular weight test method
Testing was performed using a Waters 2695 Isocratic HPLC gel chromatograph (differential refractive detector 2141). 3.0% by mass of polyphenylEthylene solution sample is used as reference, and matched chromatographic column is selected. Preparing a 3.0% polymer solution by using a purified N-methyl pyrrolidone (NMP) solvent, and standing the prepared solution for one day for later use. During the test, tetrahydrofuran is firstly sucked by a syringe, and then the syringe is washed, and the test is repeated for several times. Then, 5ml of the test solution was aspirated, the air in the syringe was removed, and the needle tip was wiped dry. And finally, slowly injecting the sample solution into the sample inlet. And obtaining data after the indication is stable.
Glass transition temperature test method
The test was performed using a Differential Scanning Calorimeter (DSC), relaxation/DSC 200F3/STA449F 3.
Preparing an adhesive film, and weighing about 30mg of samples; the alumina crucible with the sample is lightly placed at the sample position of the bracket, the temperature is raised to 60 ℃ at the temperature raising rate of 5 ℃/min, then the temperature is naturally lowered to-30 ℃, and the temperature is secondarily raised to 60 ℃ at the same temperature raising rate. And collecting data and drawing a heat flow curve. The glass transition temperature is determined from the curve.
Table 1: the types of monomers added, the amounts added (in parts by weight) and the weight percentage (wt%) with respect to the total monomer addition in examples 1 to 14
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Remarks: the symbol "/" indicates that no corresponding monomer was added.
Here, "monomer (I)", "monomer (II)", "monomer (III)", "monomer (IV)", "monomer (V)", and "monomer (VI)" respectively represent a monomer corresponding to the structural unit represented by formula (I), a monomer corresponding to the structural unit represented by formula (II), a monomer corresponding to the structural unit represented by formula (III), a monomer corresponding to the structural unit represented by formula (IV), a monomer corresponding to the structural unit represented by formula (V), and a monomer corresponding to the structural unit represented by formula (VI).
The abbreviations in Table 1 have the meanings given below:
TEOS: vinyl triethoxysilane
VTMOS: vinyl trimethoxy silane
2-EHA: isooctyl acrylate
EA: acrylic acid ethyl ester
BA: butyl acrylate
MMA: methyl methacrylate
HEA: hydroxy ethyl acrylate
Performance and test results
(one) coating Window test
The coating window refers to the maximum coating quality of a single surface per unit area of the negative electrode slurry on the pole piece under the condition that the pole piece is not cracked.
Coating Window test of adhesive of example 1
The negative electrode active material graphite, conductive carbon as a conductive agent, carboxymethylcellulose sodium CMC-Na as a stabilizer, and the binder in example 1 were weighed in the weight ratio shown in table 2 (the binder content in example 1 was increased from 1.2% to 2.2%) and stirred in deionized water to obtain each negative electrode slurry. The solid content in each negative electrode slurry was 40%.
The prepared negative electrode slurry was uniformly coated on a negative electrode current collector copper foil by the same extrusion coater at a coating speed of 50m/min. The specific coating modes are as follows.
160mg/1540 on one side.25mm 2 For initial coating quality, 10mg/1540.25mm 2 The coating quality is gradually increased in units of increase. And drying the coated negative electrode plate, and then observing whether the negative electrode plate is cracked or not. If cracking occurs, the previous coating quality is taken as the maximum coating quality. If not, the coating quality is increased continuously until cracking is observed. The maximum coating quality of the negative electrode slurry thus prepared was measured, and the test results are shown in table 2.
Coating Window test of the adhesive of examples 1 to 14 and comparative example 1
The binders of examples 1 to 14 and the binder of comparative example 1 were used to prepare negative electrode pastes, respectively, and the maximum coating quality per unit area was achieved without cracking of the electrode sheet when the binder contents were tested to be 1.2% and 2.2%, respectively. When the content of the binder is 1.2%, uniformly mixing 97% of graphite, 1.2% of binder, 1.2% of CMC-Na and 0.6% of conductive carbon of the conductive agent by weight percent, and dispersing in deionized water to form negative electrode slurry; when the binder content is 2.2%, graphite, the binder, CMC-Na and conductive carbon of the conductive agent are uniformly mixed according to the weight percentage of 96 percent to 2.2 percent to 1.2 percent to 0.6 percent and then dispersed in deionized water to form the negative electrode slurry. The solid content of the negative electrode slurry was 40%.
The prepared negative electrode slurry was uniformly coated on a negative electrode current collector copper foil by the same extrusion coater at a coating speed of 50m/min. The specific coating modes are as described above. The maximum coating quality of the negative electrode slurry thus prepared was measured, and the test results are shown in table 3.
(II) testing of adhesive force and cohesive force of negative electrode plate
The negative electrode active material graphite, conductive carbon, stabilizer sodium carboxymethylcellulose CMC-Na, the binders in examples 1 to 14, and the binder in comparative example 1 were prepared, respectively, as negative electrode pastes, wherein the weight percentage of graphite, binder, CMC-Na, and conductive agent was 97%:1.2%:1.2%:0.6%, i.e., the content of the binder was 1.2% relative to the total solid content of the negative electrode paste. Uniformly coating the prepared negative electrode slurry on a negative electrode current collector copper foil by using the same coating machine, wherein the coating quality is 160mg/1540.25mm 2 Drying and cold pressing to obtain the negative pole piece,the thus prepared negative electrode sheet was tested for adhesion and cohesion. The test results are shown in table 3.
Negative pole piece related parameter test
1. Negative pole piece adhesion testing process
Equipment model: zhongzhi detection tensile machine (model LXG 2-LLCS-0009), specific test flow:
taking a pole piece to be tested, and cutting the width by a bladeThe double-sided adhesive tape with the length of 90-150 mm is adhered to a steel plate, and the size of the adhesive tape is the width +.>The length is 90-150 mm. And (5) sticking the cut pole piece adhesive tape on the double-sided adhesive tape with the test surface facing upwards. And rolling three times in the same direction by using a pressing roller. And (3) turning on a power supply of the tension machine, fixing one end of the steel plate, which is not attached with the pole piece, by using a lower clamp, and ensuring that the steel plate is vertically placed with the base, wherein the bottom end of the steel plate is flush with the base. And (3) turning up the pole piece stuck on the steel plate, and fixing the pole piece by using an upper clamp. Pre-stretching by about 5mm, resetting the force and displacement parameters, and after the force and displacement parameters are reset to zero, clicking a start button to start the test, and recording the test result. The test was repeated three times and the average N1 (unit: N/20 mm) was calculated and the final adhesion size = = ->. The test results are shown in table 3.
2. Negative pole piece cohesion testing process
Taking a pole piece to be tested, and cutting the width by a bladeThe double-sided adhesive tape with the length of 90-150 mm is adhered to a steel plate, and the size of the adhesive tape is the width +.>The length is 90-150 mm. And (5) sticking the cut pole piece adhesive tape on the double-sided adhesive tape with the test surface facing upwards. The low-viscosity green with the width of 20mm and the length of 80-200 mm larger than the length of the adhesive tapeThe adhesive tape is flatly adhered to the surface of the test surface, and is rolled three times along the same direction by a pressing roller. And (3) turning on a power supply of the tension machine, fixing one end of the steel plate, which is not attached with the pole piece, by using a lower clamp, and ensuring that the steel plate is vertically placed with the base, wherein the bottom end of the steel plate is flush with the base. And (3) turning up the green glue adhered with the hard paper, and fixing by using an upper clamp. Pre-stretching by about 5mm, resetting the force and displacement parameters, and after the force and displacement parameters are reset to zero, clicking a start button to start the test, and recording the test result. The test was repeated three times and averaged for N1 (unit: N/20 mm) and the final cohesion magnitude =. The test results are shown in table 3.
(III) Battery Performance test
Preparation of negative electrode plate
The negative electrode active material graphite, conductive carbon, stabilizer sodium carboxymethylcellulose CMC-Na, the binders in examples 1 to 14, and the binder in comparative example 1 were prepared, respectively, as negative electrode pastes, wherein the weight percentage of graphite, binder, CMC-Na, and conductive agent was 97%:1.2%:1.2%:0.6%, i.e., the content of the binder was 1.2% relative to the total solid content of the negative electrode paste. Uniformly coating the prepared negative electrode slurry on a negative electrode current collector copper foil by using the same coating machine, wherein the coating quality is 160mg/1540.25mm 2 And drying and cold pressing to prepare the negative electrode plate.
Preparation of positive electrode plate
The positive electrode active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Stirring and dispersing conductive agent Super-P and binder polyvinylidene fluoride in the mass ratio of 96:2:2 in N-methyl pyrrolidone to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector aluminum foil, and compacting by a cold press to obtain a positive electrode plate.
Preparation of electrolyte
Adding lithium salt LiPF into a mixed solvent of Ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) with the mass ratio of 35:65 6 And uniformly mixing to obtain the electrolyte. LiPF in electrolyte 6 The molar concentration of (2) was 1mol/L.
Isolation film
The isolating film is a porous polyethylene film with the thickness of 12 mu m.
Preparation of lithium ion batteries
And stacking the prepared negative electrode plate, the isolating film and the positive electrode plate in sequence, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, winding to obtain a bare cell, inserting the bare cell into a battery shell, and performing procedures of baking, liquid injection, standing, packaging, formation, capacity division and the like to obtain the lithium ion battery.
Battery performance test
1. Battery DCR performance test
The test process of the normal temperature DCR@25deg.C is as follows: at 25 ℃, the battery is charged to 4.3V at a constant current of 0.33C, then charged to 0.05C at a constant voltage of 4.3V, left for 60s, then discharged to soc=50% (remaining capacity) at 0.33C, after 5min of rest, the voltage V1 is recorded, then discharged for 30s at 3C, the voltage V2 is recorded, and then the dcr@25deg.c= (V1-V2)/3C of the battery.
The test process of the low-temperature DCR@25 ℃ is as follows: at 25 ℃ (charging at room temperature), the battery is charged to 4.3V at a constant current of 0.33C, then charged to 0.05C at a constant voltage of 4.3V, left to stand for 60s, then discharged to soc=50% at 0.33C, after leaving at-25 ℃ for 2 hours, the voltage V3 is recorded, then discharged at 0.36C for 30s, the voltage V4 is recorded, and the dcr@25 ℃ = (V3-V4)/0.36C of the battery is obtained.
2. Battery cycle performance test
The cycle performance test process of the lithium ion battery is as follows: charging lithium ion battery to 4.25V at constant current of 0.33C under constant temperature of 25deg.C, 45 deg.C and 60deg.C, charging to current of 0.05C at constant voltage of 4.25V, discharging to 2.8V at constant current of 0.33C to obtain first-turn discharge specific capacity (C 0 ). Repeating the charge and discharge until 500 th circle to obtain discharge specific capacity after 500 circles of circulation, which is marked as C n 。
Capacity retention = specific discharge capacity after 500 cycles (C n ) Specific discharge capacity of first turn (C 0 )。
3. Storage performance test of lithium ion battery
The storage performance test process of the lithium ion battery is as follows:
charging lithium ion battery at 25deg.C under constant current of 0.33C to 4.25V, constant voltage charging to current of 0.05C, and constant current discharging to 0.33C to 2.8V to obtain initial specific discharge capacity (C 0 ）。
Thereafter, the battery was charged to 4.25V at a constant current of 0.33C at a temperature of 25℃, and then charged at a constant voltage until the current became 0.05C, and placed in a furnace having a constant temperature of 45℃. Taking out the battery after 120 days of storage, standing for 12h at 25deg.C, starting to test capacity, discharging to 2.8V with constant current of 0.33C to obtain discharge specific capacity (C) after 120 days of storage n ）。
Capacity retention = specific discharge capacity after 120 days of storage (C n ) Specific discharge capacity (C) 0 )。
The test results of the above battery performance are shown in table 4.
Table 2 a negative electrode slurry was prepared using the binder of example 1, and the binder content was tested to increase from 1.2% to 2.2% and the maximum coating quality per unit area that can be achieved without cracking of the electrode sheet was referred to herein as the coating window.
Table 2: negative electrode slurry prepared using the binder of example 1 and coating window thereof
The test results are shown in the last column of table 2. The results show that in the case of a binder content varying from 1.2% to 2.2%, the maximum coating quality showed a substantially increasing trend with increasing binder content, in particular from 210 mg/1540.25mm 2 Increased to 290mg/1540.25mm 2 . This shows that within the range of binder contents tested, the maximum coating quality is related to the binder content in the negative electrode slurry, the higher the binder content, the greater the maximum coating quality that can be achieved.
Table 3 the binders of examples 1 to 14 and the binder of comparative example 1 were used to prepare negative electrode pastes, and the maximum coating quality per unit area (i.e., coating window) that can be achieved without cracking of the electrode sheet was tested at binder contents of 1.2% and 2.2%, respectively. When the content of the binder is 1.2%, uniformly mixing 97% by weight of graphite, 1.2% by weight of the binder, 1.2% by weight of CMC-Na and 0.6% by weight of the conductive agent, and dispersing in deionized water to form negative electrode slurry; when the binder content is 2.2%, graphite, the binder, CMC-Na and the conductive agent are uniformly mixed according to the weight percentage of 96 percent to 2.2 percent to 1.2 percent to 0.6 percent and then dispersed in deionized water to form the negative electrode slurry. Among them, the binder of comparative example 1 is a binder polyacrylic acid (PAA) commonly used in the art.
The binders of examples 1 to 14 and the binder of comparative example 1 were also used in table 3 to prepare negative electrode pastes, wherein the content of the binder was 1.2%. At 160mg/1540.25mm 2 The coating quality of the above was used to prepare a negative electrode sheet, and the adhesive force and cohesive force of the negative electrode sheet prepared thereby were tested.
Table 3: coating window of each adhesive and adhesive force and cohesive force of negative electrode plate
As can be seen from table 3, the maximum coating quality on the current collector was increased by the negative electrode pastes prepared using the binders of examples 1 to 14 of the present application, as compared with the binder of comparative example 1. Similarly, the adhesive force and cohesive force of the negative electrode sheets prepared using the adhesives of examples 1 to 14 of the present application were increased to different degrees as compared with the adhesive agent of comparative example 1. These results show that the adhesive can reduce or eliminate stress accumulation in the pole piece, enhance the adhesive force and cohesive force of the pole piece, further improve the thick coating performance of the negative electrode slurry on the current collector, and realize that the pole piece is not cracked during thick coating.
Table 4: is an electrochemical performance test of the secondary battery.
As can be seen from table 4, the batteries using the binders of examples 1 to 14 of the present application were more excellent in capacity retention after 120 days of storage at 25 ℃ and 45 ℃ and 60 ℃ in terms of the direct current resistance at 25 ℃ and-25 ℃ for 500 cycles, compared to the batteries using the binders of comparative example 1. This shows that the use of the binder of the present application helps to reduce the direct current resistance, increase the electron transfer rate, and further improve the cycle performance and storage performance of the battery.
From the above results, it is clear that the binders of examples 1 to 14 of the present application have excellent adhesion as compared to the binder of comparative example 1, and further the maximum coating quality of the pole pieces prepared using these binders is higher, and it is possible to realize thick coating without cracking, thereby improving the energy density of the battery.
Regarding the electrochemical performance, the normal temperature/low temperature DCR of the battery prepared by using the binder of the embodiments 1-14 is obviously improved, so that the charge and discharge efficiency of the battery can be improved, and the service life of the battery can be prolonged. The storage capacity retention rates of 500 circles of normal temperature/high temperature circulation and 120 days of high temperature storage are superior to those of the comparative example, and the practical application scene of the battery is widened.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (14)
1. An adhesive comprising a polymer comprising a structural unit represented by formula (I) and a structural unit represented by formula (II) and a structural unit represented by formula (III), and at least one selected from a structural unit represented by formula (IV), a structural unit represented by formula (V) or a structural unit represented by formula (VI);
，/>，/>，
、/>、/>；
wherein,
r1, R2, R4, R6, R7 are each independently selected from H, unsubstituted or substituted C 1 -C 20 Alkyl, unsubstituted or substituted C 1 -C 20 At least one of alkoxy groups, wherein the substituted C 1 -C 20 Substituent groups in alkyl groups and said substituted C 1 -C 20 The substituent groups in the alkoxy groups are respectively and independently selected from at least one of hydroxyl, halogen or amino;
r3 and R5 are each independently selected from unsubstituted or substituted C 1 -C 20 At least one of alkyl groups, said substituted C 1 -C 20 The substituent group in the alkyl group is selected from at least one of hydroxyl, halogen or amino.
2. The binder of claim 1 wherein R1, R2, R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of alkyl groups;
and/or R3 is selected from unsubstituted C 1 -C 4 At least one of alkyl groups;
and/or R5 is selected from unsubstituted or substitutedC 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group.
3. The adhesive according to claim 1 or 2, wherein the polymer comprises at least one structural unit represented by formula (IV), wherein R4 is selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group.
4. The adhesive according to claim 1 or 2, wherein the polymer comprises at least one structural unit represented by formula (IV) and at least one structural unit represented by formula (V), wherein R4, R6 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group.
5. The adhesive according to claim 1 or 2, wherein the polymer comprises at least one structural unit represented by formula (IV), at least one structural unit represented by formula (V) and at least one structural unit represented by formula (VI), wherein R4, R6, R7 are each independently selected from H, unsubstituted C 1 -C 4 At least one of the alkyl groups, R5 is selected from unsubstituted or substituted C 1 -C 8 At least one of alkyl groups, said substituted C 1 -C 8 The substituent in the alkyl group is a hydroxyl group.
6. The adhesive according to claim 1 or 2, wherein in the polymer, the mass percentage of the structural unit represented by formula (I) is 4.5 to 8%, the mass percentage of the structural unit represented by formula (II) is 12 to 21%, the mass percentage of the structural unit represented by formula (III) is 3 to 6.5%, and the mass percentage of at least one selected from the structural unit represented by formula (IV), the structural unit represented by formula (V), or the structural unit represented by formula (VI) is 68 to 77%.
7. The adhesive according to claim 1 or 2, wherein the glass transition temperature of the polymer is-15 ℃.
8. The adhesive according to claim 1 or 2, wherein the weight average molecular weight of the polymer is 40-100 ten thousand.
9. A method of preparing the adhesive of any one of claims 1 to 8, comprising:
adding a monomer corresponding to a structural unit represented by the formula (I) and a monomer corresponding to a structural unit represented by the formula (II) into a solvent, and reacting in the presence of a first surfactant and a first initiator to prepare a first emulsion;
adding a monomer corresponding to a structural unit represented by formula (III) and at least one monomer selected from a monomer corresponding to a structural unit represented by formula (IV), a monomer corresponding to a structural unit represented by formula (V) or a monomer corresponding to a structural unit represented by formula (VI) into a first emulsion, and reacting in the presence of a second surfactant to prepare a second emulsion;
and heating the second emulsion, and reacting in the presence of a second initiator to obtain the adhesive.
10. A negative electrode tab comprising a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, the negative electrode film layer comprising the binder of any one of claims 1 to 8, or the binder prepared by the method of claim 9.
11. The negative electrode tab of claim 10, wherein the binder is present in an amount of 1.2% -2.2% by mass of the total mass of the negative electrode film layer.
12. The negative electrode tab of claim 10 or 11, wherein the negative electrode film layer further comprises a stabilizer comprising at least one of sodium carboxymethyl cellulose, sodium alginate, or sodium cyclodextrin.
13. A battery comprising the negative electrode tab of any one of claims 10 to 12.
14. An electrical device comprising the battery of claim 13.
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