CN116375923A - Aqueous adhesive for lithium ion battery and preparation method thereof - Google Patents
Aqueous adhesive for lithium ion battery and preparation method thereof Download PDFInfo
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- CN116375923A CN116375923A CN202211330178.3A CN202211330178A CN116375923A CN 116375923 A CN116375923 A CN 116375923A CN 202211330178 A CN202211330178 A CN 202211330178A CN 116375923 A CN116375923 A CN 116375923A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 67
- 239000000853 adhesive Substances 0.000 title claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 161
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 52
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000003999 initiator Substances 0.000 claims description 34
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000012966 redox initiator Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- 239000005077 polysulfide Substances 0.000 claims description 4
- 150000008117 polysulfides Polymers 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229920000642 polymer Polymers 0.000 abstract description 20
- 239000007772 electrode material Substances 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 64
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 21
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 16
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 101150016402 fsn-1 gene Proteins 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the technical field of aqueous adhesives, and particularly provides a lithium ion battery aqueous adhesive and a preparation method thereof. The aqueous binder for the lithium ion battery comprises 1-50% by weight of polyacrylate shown as structural formula A-B-C, wherein the hydrophilicity of a A, B, C chain segment structure is sequentially enhanced, the hydrophobicity is sequentially reduced, and the aqueous binder is prepared from a polymer represented by a molecular formula CH 2 =CR 1 R 2 Represented hydrophilic monomers and formula CH 2 =CR 3 R 4 The hydrophobic monomer is obtained by polymerization according to different composition proportion distribution. The aqueous binder for the lithium ion battery has good dispersion performance and good cohesiveness to electrode materials, and can improve the electrical performance of the lithium ion battery.
Description
Technical Field
The application relates to the technical field of aqueous adhesives, in particular to a lithium ion battery aqueous adhesive and a preparation method thereof.
Background
In the preparation of the electrode sheet of the lithium ion battery, the adhesive and the electrode active material are required to be dispersed and uniformly mixed, then coated on a current collector such as a copper foil, and finally the electrode sheet is prepared through treatment processes such as drying. The binder is an inactive substance in the electrode material, but plays a critical role in the electrochemical performance of the electrode sheet and ultimately the lithium ion battery.
The binder has the main function of connecting the electrode active material, the conductive agent and the electrode current collector, so that the electrode active material, the conductive agent and the current collector have integral connectivity, and the impedance of the electrode is reduced. The requirements of the adhesive with good performance are as follows: (1) environmental protection and safety, and water is the best solvent; (2) good adhesive property; (3) good dispersibility, can better stabilize electrode material; (4) electrochemical stability, electrolyte swelling resistance; (5) has better flexibility.
The better performance of the adhesive is the research direction continuously explored by researchers in the industry, so that the performance of the lithium ion battery can be further improved.
Disclosure of Invention
The polyacrylate aqueous adhesive has good adhesive property, electrochemical stability and electrolyte swelling resistance, and can obtain better flexibility after structural adjustment, but the dispersibility of the electrode material also needs to be improved, and particularly the electrode material with different particle shapes and surface chemical structures needs to have better dispersibility. The polyacrylate aqueous binders currently used in the market also have to be formulated with sodium carboxymethylcellulose, the latter providing the necessary dispersing capacity of the electrode material.
In order to solve the technical problem of insufficient dispersibility of polyacrylate aqueous adhesive to electrode active materials, the application provides a lithium ion battery aqueous adhesive and a preparation method thereof.
The application adopts the following technical scheme:
a lithium ion battery water-based adhesive comprises 1-50% by weight of polyacrylate with a structural formula shown in a formula (1),
A-B-C(1)
wherein A represents a structure represented by formula (2),
c represents a structure shown in formula (3),
b represents a transition structure between A and C,
wherein R is 1 And R is 3 Independently selected from H or C1-C4 alkyl, R 2 Selected from the group consisting of C1-C18 carboxylates, C1-C18 sulfonates, C1-C18 sulfates, C1-C18 phosphates, hydroxyl-containing C1-C4 substituted alkyl groups, amine-containing C1-C4 substituted alkyl groups, carboxyl-containing C1-C8 substituted alkyl groups, and CONR of formula 5 R 6 The amide group or formula of (C) is COO (CH) 2 CH 2 O) m R 7 Polyether modified esters, wherein R 5 And R is 6 Independently selected from H, methyl or ethyl, R 7 Selected from H, C-C4 alkyl or C1-C4 substituted alkyl, m=1-30, R 4 Selected from COOR of formula 8 An ester group, a phenyl group, a substituted phenyl group or a nitrile group, wherein R 8 Is C1-C22 alkyl, a is more than 0, b is more than 0, C is more than 0, d is more than or equal to 0,0.1 and less than or equal to b/(a+b) and less than or equal to 0.9, d/(c+d) and less than or equal to 0.2, (c+d): (a+b) =1:9-9:1.
Preferably, the weight ratio of the polyacrylate in the aqueous adhesive is 5-30%.
Preferably, the value of b/(a+b) is not less than 0.25 and not more than 0.65.
Preferably, the value of d/(c+d) is not higher than 0.15.
Preferably, the ratio of (c+d): (a+b) =2:8-8:2.
Preferably, the ratio of (c+d): (a+b) =4:6-6:4.
The method for preparing the aqueous binder for the lithium ion battery according to any one of the above embodiments, comprising the following steps:
s1, respectively adopting the molecular formula CH 2 ＝CR 1 R 2 Represented hydrophilic monomers and formula CH 2 ＝CR 3 R 4 The represented hydrophobic monomer is divided into two parts; r is R 1 、R 2 、R 3 、R 4 The meaning of (2) is as above;
s2, mixing a first part of hydrophilic monomers and a first part of hydrophobic monomers, adding the mixture into water, heating to a reaction temperature, dropwise adding a first water-soluble initiator solution, continuously reacting for 0-8 hours after dropwise adding, dropwise adding a second part of hydrophilic monomers and a second part of hydrophobic monomers, and cooling after dropwise adding to obtain the lithium ion battery water-based adhesive.
Preferably, the first water-soluble initiator is selected from one or a plurality of compositions of a polysulfide initiator, a peroxide initiator, an azo initiator and a redox initiator, and the dosage of the first water-soluble initiator is 0.05-1.0% of the sum of the weight of the hydrophilic monomer and the weight of the hydrophobic monomer.
Preferably, a second water-soluble initiator solution is added dropwise while adding a second part of the hydrophilic monomer and a second part of the hydrophobic monomer, and the amount of the second water-soluble initiator is 0.05-0.3% of the sum of the weights of the hydrophilic monomer and the hydrophobic monomer.
Preferably, the time for dropping the second part of the hydrophilic monomer and the second part of the hydrophobic monomer is 30 minutes to 8 hours.
In summary, the present application has the following beneficial effects:
1. three different chain segment structures exist in the polyacrylate structure, the A chain segment structure has good hydrophobicity, the C chain segment structure has good hydrophilicity, the hydrophilic hydrophobicity of the B chain segment structure is between the A chain segment structure and the C chain segment structure, the hydrophilic hydrophobicity of the A chain segment structure, the B chain segment structure and the C chain segment structure sequentially changes, namely, the hydrophilicity is sequentially enhanced from the A chain segment structure to the B chain segment structure to the C chain segment structure, and the hydrophobicity is sequentially deteriorated. Through the sequential arrangement of the hydrophilic and hydrophobic properties of the A, B, C chain segment structures in the polyacrylate, the aqueous binder has good dispersibility on active substances and the like of electrode materials and good adhesive force on a current collector while achieving good cohesiveness.
2. The application adopts a 2-stage polymerization method, and has simple process and easy operation. Meanwhile, in the 2-stage polymerization method, a polymer chain segment structure A with higher hydrophobic monomer content is obtained in the polymerization process of the first stage, and the chain segment structure A is more prone to be adsorbed on the surface of particles with higher hydrophobicity, such as carbon black conductive agent in a cathode slurry formula; the monomers added in the polymerization part of the first stage and the second stage have a coexistence period (namely, a transition structure represented by a polymerized chain segment B is formed), and the proportion of the hydrophobic monomers in the polymer chain obtained in the polymerization process is gradually reduced. The polymeric chain segment B has good adsorption performance on graphite particles with weak hydrophobicity, so that the dispersion of the graphite particles can be realized; and the hydrophobic monomer in the obtained polymer chain segment structure C is less, the content of hydrophilic monomer is higher, the hydrophilicity of the chain segment structure C is strong, and the polymer chain segment structure C can be better adsorbed with a current collector copper foil, so that better bonding effect is brought.
3. Compared with the existing polyacrylate aqueous adhesive, the aqueous adhesive has the advantages that the sufficient peeling strength between the aqueous adhesive and a current collector is met, meanwhile, the stacking density of the pole piece is higher, the internal resistance is lower, the capacity of the prepared lithium ion battery is higher, and the internal resistance of the battery is lower.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
In one aspect, the application provides a lithium ion battery water-based adhesive, which comprises 1-50% by weight of polyacrylate with a structural formula shown as a formula (1),
A-B-C(1)
wherein A represents a structure represented by formula (2),
c represents a structure shown in formula (3),
b represents a transition structure between A and C,
in the polyacrylate structure, -CH 2 -CR 1 R 2 -a polymeric monomer CH corresponding to the segment 2 ＝CR 1 R 2 Providing hydrophilicity to the polyacrylate; -CH 2 -CR 3 R 4 -a polymeric monomer CH corresponding to the segment 2 ＝CR 3 R 4 Is a hydrophobic monomer, provides hydrophobicity to the polyacrylate. In the polyacrylate of the present application, (1) hydrophilic segment-CH among the three polymeric segments by A, B, C 2 -CR 1 R 2 -and hydrophobic segment-CH 2 -CR 3 R 4 The structure setting and the adjustment of the proportion of the hydrophilic chain segment and the hydrophobic chain segment, the hydrophilicity of the structure of the A, B, C three polymeric chain segments is sequentially enhanced, the hydrophobicity is sequentially weakened, the length proportion of the structure of the A, B, C three polymeric chain segments is adjusted, the polyacrylate achieves better hydrophilic-hydrophobic balance, the active particles of the electrode material have better dispersion performance, the current collector has better adhesive performance, and the proportion of the hydrophilic chain segment and the hydrophobic chain segment in the polyacrylate structure and the proportion of the block structure can be correspondingly adjusted according to different surface properties of specific active particles, so that the process is flexible.
In the structural formula, R 1 And R is 3 Independently selected from H or C1-C4 alkyl; r is R 2 Is hydrophilic and can be selected from carboxylate of C1-C18, and C1-C18Sulfonate, C1-C18 sulfate, C1-C18 phosphate, hydroxyl-containing C1-C4 substituted alkyl, amino-containing C1-C4 substituted alkyl, carboxyl-containing C1-C8 substituted alkyl, and CONR of formula 5 R 6 The amide group or formula of (C) is COO (CH) 2 CH 2 O) m R 7 Polyether modified esters, wherein R 5 And R is 6 Independently selected from H, methyl or ethyl, R 7 Selected from H, C-C4 alkyl or C1-C4 substituted alkyl, m=1-30; r is R 4 Is hydrophobic and is selected from COOR 8 An ester group, a phenyl group, a substituted phenyl group or a nitrile group, wherein R 8 Is C1-C22 alkyl, a is more than 0, b is more than 0, C is more than 0, d is more than or equal to 0,0.1 and less than or equal to b/(a+b) and less than or equal to 0.9, d/(c+d) and less than or equal to 0.2,
(c+d):(a+b)＝1:9-9:1。
in the present application, the above-mentioned B structure is also represented by-CH 2 -CR 1 R 2 -and-CH 2 -CR 3 R 4 -composition, -CH 2 -CR 1 R 2 Segment and CH 2 -CR 3 R 4 The molar ratio of the segments is between the value of B/a in the A-segment structure and the value of d/C in the C-segment structure, i.e.the B-segment structure corresponds to the transition structure of the A-and C-polymeric segment structures. Namely, the-CH in the B structure is set 2 -CR 1 R 2 -mole number of segments e, -CH 2 -CR 3 R 4 The number of moles of segments is f, b/a > f/e > d/c.
In the present application, further, the weight ratio of polyacrylate in the aqueous binder is 5 to 30%. By adjusting the weight ratio of polyacrylate in the aqueous adhesive, the viscosity (25 ℃) of the aqueous adhesive is between 500 and 50000mPa.s, and the aqueous adhesive is suitable for operation. Further, the viscosity (25 ℃) of the aqueous adhesive is between 1500 and 25000 mPa.s.
In the present application, further, the value of b/(a+b) is not less than 0.25 and not more than 0.65. In the A polymer chain segment structure, the hydrophobicity of the A polymer chain segment structure can be adjusted by adjusting the ratio of a to b, and under the condition that the hydrophilic monomer and the hydrophobic monomer are the same, the higher the value of b/a, the stronger the hydrophobicity of the A polymer chain segment structure, the lower the value of b/a, and the poorer the hydrophobicity of the A polymer chain segment structure. When a and b are within a certain ratio, the hydrophobicity of the A polymer chain segment structure is suitable.
In the present application, further, the value of d/(c+d) is not higher than 0.15. In the structure of the C polymer chain segment, the hydrophilicity of the structure of the C polymer chain segment can be adjusted by adjusting the ratio of C to d, and under the condition that the hydrophilic monomer and the hydrophobic monomer are the same, the higher the value of d/C is, the weaker the hydrophilicity of the structure of the C polymer chain segment is, the lower the value of d/C is, and the better the hydrophilicity of the structure of the C polymer chain segment is. When C and d are in a certain proportion, the hydrophilicity of the C polymer chain segment structure is more suitable.
In this application, (c+d): (a+b) =2:8-8:2.
In this application, (c+d): (a+b) =4:6-6:4.
In the acrylic ester structure, the proportion of the A polymer chain segment structure and the C polymer chain segment structure is adjusted, so that the acrylic ester has better hydrophilic and hydrophobic properties and better dispersibility for different electrode active substances. The aqueous adhesive is applied to lithium ion batteries, and can well disperse and bond electrode active substances on current collectors.
In another aspect, the present application provides a method for preparing the aqueous binder for a lithium ion battery according to any one of the above embodiments, including the following steps:
s1, respectively adopting the molecular formula CH 2 ＝CR 1 R 2 Represented hydrophilic monomers and formula CH 2 ＝CR 3 R 4 The represented hydrophobic monomer is divided into two parts; r is R 1 、R 2 、R 3 、R 4 The meaning of (2) is as above;
s2, mixing the first part of hydrophilic monomers and the first part of hydrophobic monomers, adding the mixture into water, heating to a reaction temperature, dropwise adding the first water-soluble initiator solution, continuously reacting for 0-8 hours after the dropwise adding, dropwise adding the second part of hydrophilic monomers and the second part of hydrophobic monomers, and cooling after the dropwise adding is finished to obtain the lithium ion battery water-based adhesive.
In the application, further, the first water-soluble initiator is selected from one or a plurality of combinations of a polysulfide initiator, a peroxide initiator, an azo initiator and a redox initiator, and the dosage of the first water-soluble initiator is 0.05-1.0% of the sum of the weight of the hydrophilic monomer and the weight of the hydrophobic monomer.
In the present application, further, the persulfate initiator may be selected from ammonium persulfate, potassium persulfate, sodium persulfate, and the like; the peroxide initiator may be selected from hydrogen peroxide; the azo initiator may be selected from azobisisobutylamines hydrochloride (AIBA), azobisisobutyronium Ding Mi hydrochloride (AIBI), etc.; the redox initiator may be selected from ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium metabisulfite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, and the like.
In the application, further, a second water-soluble initiator solution is added dropwise while adding a second part of hydrophilic monomers and a second part of hydrophobic monomers, and the dosage of the second water-soluble initiator is 0.05-0.3% of the sum of the weight of the hydrophilic monomers and the weight of the hydrophobic monomers. The second water-soluble initiator may be one or a combination of a plurality of polysulfide initiator, peroxide initiator, azo initiator and redox initiator, and the second water-soluble initiator may be the same as or different from the first water-soluble initiator.
In the present application, further, the time for dropping the second partially hydrophilic monomer and the second partially hydrophobic monomer is 30 minutes to 8 hours. By controlling the dropping time of the second part of hydrophilic monomers and the second part of hydrophobic monomers, the second part of hydrophilic monomers and the second part of hydrophobic monomers can be polymerized more completely in the dropping time.
In the step S2, after the first water-soluble initiator solution is added dropwise, the reaction is continued for 0 to 8 hours, and the reaction completion degree of the first part of hydrophilic monomers and the first part of hydrophobic monomers can be controlled by controlling the reaction continuing time. The longer the reaction time is, the more completely the first part of hydrophilic monomer and the first part of hydrophobic monomer react, and before the second part of hydrophilic monomer and the second part of hydrophobic monomer are dripped, the reaction system is not reactedThe less hydrophilic and hydrophobic monomers are reacted, the closer the f/e and d/c values in the B structure are. The shorter the continuous reaction time, the more unreacted first part of hydrophilic monomer and first part of hydrophobic monomer in the reaction system, after dropwise adding the second part of hydrophilic monomer and second part of hydrophobic monomer, firstly blending the unreacted first part of hydrophilic monomer and first part of hydrophobic monomer for polymerization, and along with the continuous dropwise adding of the second part of hydrophilic monomer and second part of hydrophobic monomer, the closer the proportion of the unreacted hydrophilic monomer and the hydrophobic monomer in the reaction system to the proportion of the second part of hydrophilic monomer and the second part of hydrophobic monomer, -CH 2 -CR 3 R 4 Segment and CH 2 -CR 1 R 2 The value of the number of segments ratio f/e is close to the value of d/C in the C-segment structure.
In the present application, the hydrophilic monomer may be exemplified by Acrylic Acid (AA), methacrylic acid (MAA), sodium acrylate (AANa), lithium acrylate (AALi), sodium methacrylate (MAANa), lithium Methacrylate (MAALi), hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA), hydroxypropyl acrylate (HPA), acrylamide (AM), N-Dimethylacrylamide (DMAA), monomethoxy polyether (meth) acrylate, and the like; the hydrophobic monomer may be selected from Acrylonitrile (AN), methyl Methacrylate (MMA), methyl Acrylate (MA), ethyl Methacrylate (EMA), ethyl Acrylate (EA), lauryl Methacrylate (LMA), lauryl Acrylate (LA), stearyl Methacrylate (SMA), stearyl Acrylate (SA), isooctyl methacrylate (2-EHA), isooctyl acrylate (2-EHMA), n-Butyl Methacrylate (BMA), n-Butyl Acrylate (BA), styrene (St), p-methylstyrene, and the like.
In the method for preparing a lithium ion battery aqueous binder of the present application, the stirring speed of the reaction system in step S2 is not particularly limited, and may be 100 to 1000rpm, or further, may be 200 to 600rpm.
The aqueous binder for lithium ion batteries and the preparation method thereof of the present application will be described in detail with reference to examples, comparative examples and experimental data. Unless otherwise indicated, parts in the following examples and comparative examples are parts by weight.
Example 1
160 parts of water, 25 parts of AA monomer, 10 parts of MA monomer and 15 parts of AN monomer are sequentially added into a reaction bottle, stirring is carried out at a rotating speed of 300rpm, the temperature is raised to 65 ℃, 10 parts of ammonium persulfate solution with the concentration of 3wt% is dropwise added, and the dropwise addition is carried out for 240min; and (3) after the completion of the dropwise addition, maintaining the reaction temperature at 65 ℃, simultaneously dropwise adding AN AA solution consisting of 45 parts of AA monomer and 200 parts of water, 5 parts of AN monomer and 10 parts of ammonium persulfate solution with the concentration of 1wt%, wherein the AA solution and the AN monomer are completely dropwise added within 120 minutes, dropwise adding the ammonium persulfate solution for 150 minutes, after the completion of the dropwise addition, reducing the temperature of a reaction system to 40 ℃, and adding a small amount of water to adjust the solid content of the adhesive, so that the solid content of the aqueous adhesive is 19.9%, and the viscosity (25 ℃) is 5100 mPa.s.
Example 2
200 parts of water, 20 parts of AA monomer and stirring and dissolving at a rotating speed of 350rpm, adding sodium bicarbonate to adjust the pH to be neutral, adding 15 parts of MA monomer and 15 parts of AN monomer, stirring, heating to 70 ℃, dropwise adding 15 parts of ammonium persulfate aqueous solution with the concentration of 3wt% and dropwise adding for 300min; after the completion of the dropwise addition, the reaction temperature is kept at 70 ℃ for 2 hours, and simultaneously, a mixed solution consisting of 45 parts of AA monomer and 150 parts of water, 5 parts of AN monomer and 10 parts of ammonium persulfate solution with the concentration of 1wt% are dropwise added, the mixed solution and AN monomer are completely added after 60 minutes, the temperature of a reaction system is reduced to 40 ℃, a small amount of water is added to adjust the solid content of the adhesive, and the prepared aqueous adhesive has the solid content of 18.2% and the viscosity (25 ℃) of 4500 mPas.
Example 3
200 parts of water, 15 parts of AA monomer and stirring and dissolving at a rotating speed of 300rpm, regulating the pH to be neutral by using lithium carbonate, adding 10 parts of MA monomer and 25 parts of AN monomer, stirring, heating to 70 ℃, dropwise adding 15 parts of ammonium persulfate aqueous solution with the concentration of 2wt% and dropwise adding for 300min; at the end of the dropwise addition, the reaction temperature was kept at 70℃for 1 hour, while a mixed solution composed of 45 parts of AA monomer and 150 parts of water, 5 parts of AN monomer and 10 parts of a 1.5wt% ammonium persulfate solution were dropwise added, the dropwise addition time of the mixed solution and AN monomer was 60 minutes, and the dropwise addition time of the ammonium persulfate solution was 80 minutes. After the dripping is finished, the temperature of the reaction system is reduced to 40 ℃, and a small amount of water is added to adjust the solid content of the adhesive. The resulting adhesive had a solids content of 15.0% and a viscosity (25 ℃) of 3700 mPas.
Example 4
500 parts of water, 20 parts of AA monomer, 15 parts of BA monomer and 15 parts of AN monomer are sequentially added into a reaction bottle, stirring is carried out at the rotating speed of 450rpm, the temperature is raised to 65 ℃, 10 parts of ammonium persulfate solution with the concentration of 2wt% is dropwise added, and the dropwise addition is carried out for 240min; at the end of the dropwise addition, the reaction temperature is kept at 65 ℃, 50 parts of mixed solution of AA monomer and 200 parts of water and 10 parts of ammonium persulfate solution with the concentration of 1wt% are synchronously dropwise added, the dropwise addition time of the mixed solution is 180min, and the dropwise addition time of the ammonium persulfate solution is 200min. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 42℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 10.2% and a viscosity (25 ℃) of 2900 mPas.
Example 5
300 parts of water, 12 parts of AA monomer, 7.5 parts of AM monomer, 6 parts of EA monomer and 4.5 parts of BA monomer are sequentially added into a reaction bottle, stirring is carried out at a rotating speed of 350rpm, the temperature is raised to 70 ℃, 10 parts of sodium persulfate aqueous solution with the concentration of 1wt% is dropwise added, and the dropwise addition is carried out for 120min; at the end of the dropwise addition, the reaction temperature was maintained at 70℃and a mixed solution composed of 59.5 parts of AM monomer and 200 parts of water, 10.5 parts of EA monomer and 20 parts of aqueous ammonium persulfate solution with a concentration of 1wt% were simultaneously dropwise added for 270min and 285min. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to give an aqueous adhesive having a solid content of 15.3% and a viscosity (25 ℃) of 3500 mPas.
Example 6
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 350rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; at the end of the dropwise addition, the reaction temperature was maintained at 70℃and a mixed solution composed of 50 parts of MAA monomer and 200 parts of water and 15 parts of an aqueous ammonium persulfate solution having a concentration of 1wt% were simultaneously dropwise added over a period of 250 minutes and an aqueous ammonium persulfate solution was dropwise added over a period of 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.1% and a viscosity (25 ℃) of 3800 mPas.
Example 7
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 300rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; at the end of the dropwise addition, the reaction temperature was maintained at 70℃and a mixed solution composed of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous solution of ammonium persulfate having a concentration of 1% by weight were simultaneously dropwise added for 250 minutes and for 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.1% and a viscosity (25 ℃) of 3600 mPas.
Example 8
In example 7, a mixed solution of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous solution of ammonium persulfate having a concentration of 1% by weight were simultaneously added dropwise, and the mixed solution of 45 parts of MAA monomer and 200 parts of water, 5 parts of BA monomer and 15 parts of an aqueous solution of ammonium persulfate having a concentration of 1% by weight were adjusted so as to be simultaneously added dropwise, and the remaining steps remained unchanged, to obtain an aqueous adhesive having a solids content of 15.0% and a viscosity (25 ℃) of 3500 mPa.s.
Example 9
In example 7, 35 parts of MAA monomer and 15 parts of EA monomer were added in this order, and the mixture was adjusted to 32.5 parts of MAA monomer and 17.5 parts of EA monomer, and the remaining steps were kept unchanged, so that the aqueous adhesive was prepared to have a solids content of 15.1% and a viscosity (25 ℃) of 3500 mPas.
Example 10
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 300rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; after the completion of the dropwise addition, the reaction was carried out at a reaction temperature of 70℃for 2 hours, and a mixed solution composed of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous ammonium persulfate solution having a concentration of 1% by weight were simultaneously dropwise added over a period of 250 minutes and an aqueous ammonium persulfate solution was dropwise added over a period of 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.0% and a viscosity (25 ℃) of 3700 mPas.
Example 11
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 300rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; after the completion of the dropwise addition, the reaction was carried out at a reaction temperature of 70℃for 4 hours, and a mixed solution composed of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous ammonium persulfate solution having a concentration of 1% by weight were simultaneously dropwise added over a period of 250 minutes and an aqueous ammonium persulfate solution was dropwise added over a period of 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.0% and a viscosity (25 ℃) of 3800 mPas.
Example 12
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 300rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; after the completion of the dropwise addition, the reaction was carried out at a reaction temperature of 70℃for 6 hours, and a mixed solution composed of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous ammonium persulfate solution having a concentration of 1% by weight were simultaneously dropwise added over a period of 250 minutes and an aqueous ammonium persulfate solution was dropwise added over a period of 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 14.9% and a viscosity (25 ℃) of 3700 mPas.
Comparative example 1
450 parts of water, 82.5 parts of MAA monomer, 15 parts of EA monomer and 2.5 parts of BA monomer are sequentially added into a reaction bottle, stirring is carried out at a rotating speed of 300rpm, the temperature is raised to 65 ℃, 50 parts of ammonium persulfate aqueous solution with the concentration of 1wt% is dropwise added, and the dropwise addition is carried out for 120min; after the dripping is finished, the temperature is increased to 75 ℃, the temperature is kept for 90min, the temperature of the reaction system is reduced to 40 ℃, and a small amount of water is added to adjust the solid content of the adhesive. The adhesive thus obtained had a solids content of 15.0% and a viscosity (25 ℃) of 3500 mPas.
Comparative example 2
450 parts of water, 82.5 parts of MAA monomer, 15 parts of EA monomer and 2.5 parts of BA monomer are sequentially added into a reaction bottle, the pH is regulated to be neutral, stirring is carried out at a rotating speed of 300rpm, the temperature is raised to 65 ℃, 50 parts of ammonium persulfate aqueous solution with the concentration of 1wt% is dropwise added, and the dropwise addition is carried out for 120min; after the dripping is finished, the temperature is increased to 75 ℃, the temperature is kept for 90min, the temperature of the reaction system is reduced to 40 ℃, and a small amount of water is added to adjust the solid content of the adhesive. The resulting adhesive had a solids content of 15.1% and a viscosity (25 ℃) of 3900 mPas.
Comparative example 3
450 parts of water and 82.5 parts of MAA monomer are added into a reaction bottle, stirring is carried out at a rotating speed of 300rpm, the temperature is raised to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% is dropwise added, and the dropwise addition is carried out for 100min; at the end of the dropwise addition, the reaction temperature was maintained at 70℃and 15 parts of EA monomer, 2.5 parts of BA monomer and 15 parts of an aqueous ammonium persulfate solution with a concentration of 1wt% were simultaneously dropwise added, the dropwise addition time of the EA monomer and BA monomer was 250 minutes and the dropwise addition time of the aqueous ammonium persulfate solution was 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.1% and a viscosity (25 ℃) of 3600 mPas.
Comparative example 4
250 parts of water and 35 parts of MAA monomer and 15 parts of EA monomer are sequentially added into a reaction bottle, stirred at a rotating speed of 300rpm, heated to 70 ℃, 25 parts of sodium persulfate aqueous solution with the concentration of 1wt% are dropwise added, and the mixture is dropwise added for 100min; after the completion of the dropwise addition, the reaction was carried out at a reaction temperature of 70℃for 10 hours, and a mixed solution composed of 47.5 parts of MAA monomer and 200 parts of water, 2.5 parts of BA monomer and 15 parts of an aqueous ammonium persulfate solution having a concentration of 1% by weight were simultaneously dropwise added over a period of 250 minutes and an aqueous ammonium persulfate solution was dropwise added over a period of 280 minutes. After the completion of the dropwise addition, the temperature of the reaction system was lowered to 40℃and the solid content of the adhesive was adjusted by adding a small amount of water to obtain an aqueous adhesive having a solid content of 15.2% and a viscosity (25 ℃) of 3700 mPas.
Table 1 raw material ratios of examples
The testing method comprises the following steps:
preparing a pole piece 1:
mixing the aqueous binders to be tested of examples 1-12 and comparative examples 1-4 with 50% water, dispersing for 10-20 minutes at 300rpm, adding SP conductive carbon black, stirring for 10 minutes at 150rpm, and stirring for 120 minutes at 700 rpm; the rotation speed was adjusted down to 300rpm, 50% of the negative electrode material, the violet cell FT-1, was added, dispersed for 20 minutes, and then the remaining 50% of the negative electrode material and the remaining 50% of the water were added for 30 minutes, followed by stirring at a high speed of 800rpm for 120 minutes. After the dispersion is finished, the viscosity is regulated to be between 2000 and 4000 mPa.s, and a 150-mesh filter screen is used for filtering to finish discharging. Placing copper foil on a coater, adjusting the scale of a scraper of a wet film preparation device, uniformly pouring the filtered slurry, sending into 100 ℃ environment, blowing and baking until the slurry is dried, cutting the slurry into a specification of 12.5cm multiplied by 5cm, and enabling the single-sided surface density to be 100-110g/m 2 Is a pole piece.
Bulk density test method: five points are selected in the middle and four corners of the pole piece, the thickness of the pole piece is measured and recorded by a screw micrometer, and the average thickness of the pole piece is obtained after a maximum value and a minimum value are removed, so that the stacking density=the pole piece area density/(the average thickness of the pole piece-the average thickness of the copper foil).
The pole piece resistance testing method comprises the following steps: selecting a clean glass sheet with the length of 20cm multiplied by 15cm, weighing and recording m1, uniformly pouring a filter material at one short end, uniformly coating a coating with the length of 20cm multiplied by 8cm by using a 250 mu m wet film preparation machine, and sending the glass sheet into an environment with the temperature of 100 ℃ for blast drying for 30min. The multimeter was adjusted to the appropriate range, the dried glass sheet was taken out, two current collectors were placed at the short ends, the coating resistance value was measured and recorded, and the coated glass sheet was weighed and recorded for m2, then the sheet resistance = coating resistance x (m 2-m 1).
The pole piece stripping force testing method comprises the following steps: and (5) sending the cut pole piece into a 35% RH thermostatic chamber for 30 minutes. The coating layer faces outwards, the copper foil faces inwards to attach the two pole pieces, and the pole pieces are sent into an electric roller press to be rolled to 1.6g/cm 3 Placing for 30 minutes after rolling, selecting five stainless steel plates with the specification of 12.5cm multiplied by 5cm, attaching double-sided adhesive tapes with corresponding specifications on the stainless steel plates, attaching a pole piece on the double-sided adhesive tapes in a way that a coating faces downwards, attaching a piece of masking paper tape with the width of 2.5cm on a copper foil, rolling the pole piece steel plates back and forth for one circle by an electric rolling roller with certain pressure (1 kg), using an electronic stripping machine, and testing the adhesive force of the pole piece; in the same way, the cohesive force of the pole piece can be tested by only changing the way that the pole piece is attached to the double-sided adhesive tape in an upward coating way.
The button cell is manufactured by the following steps:
the assembly sequence is from bottom to top negative electrode shell, elastic sheet, gasket, lithium sheet, electrolyte, diaphragm, electrolyte, electrode sheet and positive electrode shell.
Electrolyte composition: 1M LiPF6 in EC:DMC:EMC =1:1:1
A diaphragm: celgard 2325
Lithium sheet: kolu 15.0 x 1.0mm
The first discharge capacity, first coulombic efficiency and ac impedance were tested as follows:
capacity test 0.1C,0.005-1.5V charge and discharge; the impedance sweep was from 100kHz to 0.1Hz.
The results are shown in Table 2 below.
TABLE 2
Preparing a pole piece 2:
mixing the aqueous adhesives to be tested of examples 7-12 and comparative examples 1-4 with 50% water, dispersing for 10-20 minutes at 300rpm, adding SP conductive agent, stirring for 10 minutes at 150rpm, and stirring for 120 minutes at 700 rpm; the rotation speed is regulated to 300rpm, 50% of the negative electrode material fir FSN-1 is added, dispersed for 20 minutes, and the rest 50% of the negative electrode material and the rest 50% are added% water was dispersed for 30 minutes followed by high speed stirring at 800rpm for 120 minutes. After the dispersion is finished, the viscosity is regulated to be between 2000 and 4000 mPa.s, and a 150-mesh filter screen is used for filtering to finish discharging. Placing copper foil on a coater, adjusting the scale of a scraper of a wet film preparation device, uniformly pouring the filtered slurry, sending into 100 ℃ environment, blowing and baking until the slurry is dried, cutting the slurry into a specification of 12.5cm multiplied by 5cm, and enabling the single-sided surface density to be 100-110g/m 2 Is a pole piece.
Button cells were prepared and tested according to the above-described method for preparing button cells in the pole piece 1, and the results are shown in table 3.
TABLE 3 Table 3
From the data in table 2 and table 3, it can be seen that the aqueous binder for lithium ion battery of the present application has higher bulk density, low coating resistance and high peeling force, and the aqueous binder of the present application has better dispersion performance to electrode material and adhesion performance to current collector.
Comparing examples 7-12 above, it can be seen that the performance of the aqueous adhesive changes slightly with the adjustment of the proportions of the first partially hydrophilic monomer, the first partially hydrophobic monomer, and the second partially hydrophilic monomer, the second partially hydrophobic monomer.
Comparative example 7 and comparative examples 1-2, in which the hydrophilic monomer and the hydrophobic monomer were separately divided into two parts for mixed polymerization, the obtained aqueous adhesive had higher bulk density, lower coating resistance and higher peeling force, indicating that the aqueous adhesive of the present application was better in dispersibility for electrode materials and also better in adhesion to a current collector.
In comparative examples 7 and 3, the hydrophilic monomer and the hydrophobic monomer are separately divided into two parts for mixed polymerization, and the performance is better than the polymerization by separately dividing the hydrophilic monomer and the hydrophobic monomer into two parts.
In comparative examples 7 and 4, the time to continue the constant temperature reaction after the completion of the dropping of the first polymerization step has an influence on the performance of the aqueous adhesive, and the longer the time to continue the constant temperature reaction is, the better.
The specific embodiments of the present application are intended to be illustrative only and not to be limiting of the application, since modifications may be made to the embodiments by those skilled in the art without creative contribution as required after reading the specification, and are intended to be protected by the patent laws within the scope of the claims of the present application.
Claims (10)
1. The aqueous binder for the lithium ion battery is characterized in that: comprising 1 to 50% by weight of a polyacrylate of formula (1),
A-B-C(1)
wherein A represents a structure represented by formula (2),
c represents a structure shown in formula (3),
b represents a transition structure between A and C,
wherein R is 1 And R is 3 Independently selected from H or C1-C4 alkyl, R 2 Selected from the group consisting of C1-C18 carboxylates, C1-C18 sulfonates, C1-C18 sulfates, C1-C18 phosphates, hydroxyl-containing C1-C4 substituted alkyl groups, amine-containing C1-C4 substituted alkyl groups, carboxyl-containing C1-C8 substituted alkyl groups, and CONR of formula 5 R 6 The amide group or formula of (C) is COO (CH) 2 CH 2 O) m R 7 Polyether modified esters, wherein R 5 And R is 6 Independently selected from H, methyl or ethyl, R 7 Selected from H, C-C4 alkyl or C1-C4 substituted alkyl, m=1-30, R 4 Selected from COOR of formula 8 An ester group, a phenyl group, a substituted phenyl group or a nitrile group, wherein R 8 Is C1-C22 alkyl, a is more than 0, b is more than 0, C is more than 0, d is more than or equal to 0,0.1 and less than or equal to b/(a+b) and less than or equal to 0.9, d/(c+d) and less than or equal to 0.2, (c+d): (a+b) =1:9-9:1.
2. The aqueous binder for lithium ion batteries according to claim 1, wherein: the weight ratio of the polyacrylate in the aqueous adhesive is 5-30%.
3. The aqueous binder for lithium ion batteries according to claim 1, wherein: the value of b/(a+b) is not less than 0.25 and not more than 0.65.
4. The aqueous binder for lithium ion batteries according to claim 1, wherein: the value of d/(c+d) is not higher than 0.15.
5. The aqueous binder for lithium ion batteries according to claim 1, wherein: the ratio of (c+d): (a+b) =2:8-8:2.
6. The aqueous binder for lithium ion batteries according to claim 1, wherein: the ratio of (c+d): (a+b) =4:6-6:4.
7. A method for preparing the aqueous binder for lithium ion batteries according to any one of claims 1 to 6, which is characterized in that: the method comprises the following steps:
s1, respectively adopting the molecular formula CH 2 ＝CR 1 R 2 Represented hydrophilic monomers and formula CH 2 ＝CR 3 R 4 The represented hydrophobic monomers are each divided into two parts;
s2, mixing a first part of hydrophilic monomers and a first part of hydrophobic monomers, adding the mixture into water, heating to a reaction temperature, dropwise adding a first water-soluble initiator solution, continuously reacting for 0-8 hours after dropwise adding, dropwise adding a second part of hydrophilic monomers and a second part of hydrophobic monomers, and cooling after dropwise adding to obtain the lithium ion battery water-based adhesive.
8. The method of manufacturing according to claim 7, wherein: the first water-soluble initiator is selected from one or more of a polysulfide initiator, a peroxide initiator, an azo initiator and a redox initiator, and the dosage of the first water-soluble initiator is 0.05-1.0% of the sum of the weight of the hydrophilic monomer and the weight of the hydrophobic monomer.
9. The method of manufacturing according to claim 7, wherein: and a second water-soluble initiator solution is added dropwise while a second part of the hydrophilic monomers and a second part of the hydrophobic monomers are added dropwise, wherein the dosage of the second water-soluble initiator is 0.05-0.3% of the sum of the weights of the hydrophilic monomers and the hydrophobic monomers.
10. The method of manufacturing according to claim 7, wherein: the time for dripping the second part of the hydrophilic monomer and the second part of the hydrophobic monomer is 30 minutes to 8 hours.
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