CN115000629B - Coating, separator comprising same and battery - Google Patents
Coating, separator comprising same and battery Download PDFInfo
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- CN115000629B CN115000629B CN202210653974.4A CN202210653974A CN115000629B CN 115000629 B CN115000629 B CN 115000629B CN 202210653974 A CN202210653974 A CN 202210653974A CN 115000629 B CN115000629 B CN 115000629B
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- mass
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- coating
- petroleum resin
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- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 238000004804 winding Methods 0.000 claims abstract description 36
- 239000003208 petroleum Substances 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 150000001408 amides Chemical class 0.000 claims abstract description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000872 buffer Substances 0.000 claims abstract description 6
- 150000001721 carbon Chemical class 0.000 claims description 19
- 238000007731 hot pressing Methods 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000012858 packaging process Methods 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 3
- 230000007306 turnover Effects 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000025962 Crush injury Diseases 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a coating, and a separator and a battery comprising the coating. The coating comprises the following components: acid monomers, ester monomers, amide monomers, hydrogenated carbon-five petroleum resin, hydrogenated carbon-nine petroleum resin, surfactant, buffer, neutralizer and initiator; the ester monomers include methyl methacrylate, butyl acrylate and glycidyl methacrylate. The diaphragm comprising the coating can play a role in fixing the position of the anode and the cathode during winding, and keeps the coverage of the anode and the cathode, so that the specific position of the winding core can be maximally positioned in the packaging process, the accuracy of winding core shell entering is improved, the yield of the winding core in the packaging process is improved, the pole piece folding proportion caused by turnover aging is reduced, the primary pass rate of the battery core can be greatly improved, and the reject rate of products and the reworking rate of the battery core are reduced.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a coating, a diaphragm comprising the coating and a battery.
Background
At present, a P (VDF-HFP) coating is mainly adopted as a coating on the surface of a diaphragm for a lithium ion battery, the coating has no bonding performance under dry pressure (the dry bonding force is less than or equal to 3N/m, the adopted condition is that the temperature is 100 ℃, the pressure is 0.2MPa, and the time is 150 s), and the shaping effect on a winding core can not be achieved. If the processing technology can not make the diaphragm show obvious adhesive force during the production of the winding core, the winding core shaping and the shell-entering positioning are not facilitated, and the poor spacing and the crush injury of the winding core are greatly improved due to the failure of the winding core shell-entering positioning.
Disclosure of Invention
In order to solve the problem that the positioning success rate of the battery core in the winding process is low because the separator has no adhesive property under dry pressure, the invention provides a coating, and a separator and a battery comprising the coating. The coating has no bonding effect at normal temperature (20-40 ℃), has good bonding property at high temperature (above 45 ℃), can promote dry bonding force of the diaphragm, can fix the position of the anode and the cathode when being wound, keeps the coverage of the anode and the cathode, can maximally position the concrete position of the winding core in the packaging process, improves the accuracy of winding core in the shell, improves the yield of the winding core in the packaging process, reduces the bending proportion of the pole piece caused by turnover aging, reduces the reject ratio of products, reduces the reworking rate of the battery core, and improves the one-time passing rate of the battery core.
In the present invention, the term "dry adhesion force" refers to adhesion force between the separator and the separator, and between the separator and the positive and negative electrodes, which is not tested under electrolyte infiltration, and herein, the dry adhesion force between the separator and the separator is referred to as separator & separator dry adhesion force, and the dry adhesion force between the separator and the positive and negative electrode sheets is referred to as separator & negative electrode dry adhesion force or separator & positive electrode dry adhesion force.
The invention aims at realizing the following technical scheme:
a coating comprising the following components: acid monomers, ester monomers, amide monomers, hydrogenated carbon-five petroleum resin, hydrogenated carbon-nine petroleum resin, surfactant, buffer, neutralizer and initiator; the ester monomers include methyl methacrylate, butyl acrylate and glycidyl methacrylate.
According to an embodiment of the invention, the coating is used in the field of separators, preferably in the field of battery separators.
According to the embodiment of the invention, the dry bonding force between the coating and the anode and between the coating and the cathode is less than or equal to 3N/m before hot pressing (such as the temperature of 20-40 ℃), and the coating shows no bonding effect; after hot pressing (for example, the temperature is above 45 ℃), the coating is converted from a glass state to a high-elasticity state, and the dry adhesion between the coating and the negative electrode is above 25N/m, and the dry adhesion between the coating and the positive electrode is above 30N/m, so that the coating has very strong adhesion.
According to an embodiment of the present invention, the hot pressing is performed at a pressure of 0.2MPa to 0.5MPa (e.g., 0.2MPa, 0.3MPa, 0.4MPa, or 0.5 MPa), at a temperature of 45 ℃ to 100 ℃ (e.g., 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃), and for a time of 5s to 65s (e.g., 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 60s, or 65 s).
According to an embodiment of the present invention, the acid-based monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.
According to an embodiment of the present invention, the ester monomer further includes at least one of ethyl acrylate and isooctyl acrylate.
According to an embodiment of the present invention, the amide-based monomer is at least one selected from the group consisting of acrylamide, methacrylamide, and N-methylolacrylamide.
According to an embodiment of the present invention, the hydrogenated carbon five petroleum resin has a number average molecular weight of 300 to 3000; the softening point of the hydrogenated carbon five petroleum resin is 80-130 ℃, for example 80-85 ℃, 85-90 ℃, 90-95 ℃, 95-100 ℃, 100-105 ℃, 105-110 ℃, 110-115 ℃, 115-120 ℃, 120-125 ℃ or 125-130 ℃.
The hydrogenated carbon five petroleum resin has the main chain link of a fatty structure and has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical corrosion resistance and the like. The hydrogenated carbon five petroleum resin provides thermal bonding to the coating, which introduces properties that can allow the coating to bond at high temperatures.
According to an embodiment of the present invention, the hydrogenated carbon nine petroleum resin has a number average molecular weight of 300 to 3000; the hydrogenated nine-carbon petroleum resin has a softening point of 90 to 150 ℃, for example, 90 to 95 ℃, 95 to 100 ℃, 100 to 105 ℃, 105 to 110 ℃, 110 to 115 ℃, 115 to 120 ℃, 120 to 125 ℃, 125 to 130 ℃, 130 to 135 ℃, 135 to 140 ℃, 140 to 145 ℃ or 145 to 150 ℃.
The main chain link of the hydrogenated carbon nine petroleum resin is of a fatty structure, and has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical corrosion resistance and the like. The hydrogenated carbon nine petroleum resin provides thermal bonding to the coating, which introduces properties that can allow the coating to bond at high temperatures.
According to an embodiment of the present invention, the surfactant is at least one selected from Sodium Dodecyl Benzene Sulfonate (SDBS), sodium Dodecyl Sulfate (SDS), dodecylphenol polyoxyethylene ether (OP-10), nonylphenol polyoxyethylene ether sulfate, tween-85. The introduction of the surfactant can obviously reduce the surface tension of water, play a role in wetting, and also can enable one phase of two or more mutually-insoluble liquids to be dispersed in the other phase in a droplet shape, so as to play a role in emulsification; a stable system is formed.
According to an embodiment of the present invention, the buffer is selected from at least one of sodium bicarbonate and sodium carbonate. The introduction of the buffering agent can balance the pH value of the system, and is beneficial to emulsion polymerization.
According to an embodiment of the present invention, the neutralizing agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and ammonia water. The introduction of the neutralizing agent can maintain emulsion stability and is beneficial to storage.
According to an embodiment of the present invention, the initiator is at least one selected from ammonium persulfate and sodium persulfate.
According to an embodiment of the invention, the coating comprises the following components in parts by mass:
acid monomer: 8 to 14 parts by mass, preferably 8, 9, 10, 11, 12, 13, 14 parts by mass;
amide monomer: 3 to 7 parts by mass, preferably 3, 4, 5, 6, 7 parts by mass;
ester monomer: 17 to 33 parts by mass, preferably 17, 18, 19, 20, 21, 22, 23 parts by mass;
hydrogenated carbon five petroleum resin: 1 to 9 parts by mass, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 parts by mass;
hydrogenated carbon nine petroleum resin: 1 to 9 parts by mass, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 parts by mass;
and (2) a surfactant: 0.2 to 1 part by mass, preferably 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 part by mass;
buffering agent: 0.005 to 0.015 parts by mass, preferably 0.005, 0.01, 0.015 parts by mass;
neutralizing agent: 0.5 to 1.5 parts by mass, preferably 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5 parts by mass;
and (3) an initiator: 0.03 to 0.09 parts by mass, preferably 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 parts by mass.
According to an embodiment of the invention, the coating comprises the following components in parts by mass:
methacrylic acid: 8 to 14 parts by mass, preferably 10 parts by mass;
acrylamide: 3 to 7 parts by mass, preferably 5 parts by mass;
methyl methacrylate: 8 to 14 parts by mass, preferably 10 parts by mass;
butyl acrylate: 8 to 14 parts by mass, preferably 10 parts by mass;
glycidyl methacrylate: 1 to 5 parts by mass, preferably 3 parts by mass;
sodium Dodecyl Benzene Sulfonate (SDBS) or Sodium Dodecyl Sulfate (SDS): 0.1 to 0.5 parts by mass, preferably 0.3 parts by mass;
dodecylphenol polyoxyethylene ether (OP-10): 0.1 to 0.5 parts by mass, preferably 0.3 parts by mass;
ammonium persulfate: 0.03 to 0.09 parts by mass, preferably 0.06 parts by mass;
sodium bicarbonate: 0.005 to 0.015 parts by mass, preferably 0.01 part by mass;
ammonia water: 0.5 to 1.5 parts by mass, preferably 1 part by mass;
hydrogenation of C5 petroleum resin: 1 to 9 parts by mass, preferably 5 parts by mass;
hydrogenation of C9 petroleum resin: 1 to 9 parts by mass, preferably 5 parts by mass.
The invention also provides a preparation method of the coating, which comprises the following steps:
mixing an acid monomer, an ester monomer, an amide monomer, hydrogenated carbon five petroleum resin, hydrogenated carbon nine petroleum resin, a surfactant, a buffer, a neutralizer, an initiator and deionized water to prepare slurry; and coating and drying to form the coating.
Preferably, the method comprises the steps of:
mixing methacrylic acid, acrylamide, methyl methacrylate, butyl acrylate, glycidyl methacrylate, sodium Dodecyl Benzene Sulfonate (SDBS) or Sodium Dodecyl Sulfate (SDS), dodecylphenol polyoxyethylene ether (OP-10), ammonium persulfate, sodium bicarbonate, ammonia water, hydrogenated C5 petroleum resin, hydrogenated C9 petroleum resin and deionized water to prepare slurry; and coating and drying to form the coating.
According to the embodiment of the invention, the content of the deionized water is 44-72% of the mixed slurry.
According to an embodiment of the invention, the slurry has a solids content of about 30% to 58%.
The invention also provides a diaphragm, which comprises the coating.
According to an embodiment of the invention, the coating has an areal density of 0.2 to 1.0g/m 2 Preferably 0.4 to 0.8g/m 2 Such as 0.6g/m 2 . For example 0.2g/m 2 、0.3g/m 2 、0.4g/m 2 、0.5g/m 2 、0.6g/m 2 、0.7g/m 2 、0.8g/m 2 、0.9g/m 2 、1.0g/m 2 。
According to an embodiment of the present invention, the separator includes a separator substrate and a coating layer provided on at least one side surface of the separator substrate.
According to an embodiment of the invention, the thickness of the separator substrate is 3 μm to 20 μm, for example 3 μm, 5 μm, 8 μm, 10 μm, 15 μm, 18 μm or 20 μm.
According to an embodiment of the present invention, the separator substrate is selected from at least one of polyethylene, polypropylene, polyethylene/polypropylene composite, polyamide, polyethylene terephthalate, polybutylene terephthalate, polystyrene.
According to an embodiment of the invention, the separator further comprises a ceramic layer, which is provided on the surface of the separator substrate and/or on the surface of the coating.
The invention also provides a battery, which comprises the separator.
According to an embodiment of the present invention, the battery includes a positive electrode and a negative electrode, and the positive electrode and the negative electrode are separated by the separator described above.
According to an embodiment of the present invention, the dry adhesion between the separator and the negative electrode is 25N/m or more, and the dry adhesion between the separator and the positive electrode is 30N/m or more.
According to the embodiment of the invention, after the diaphragm and the winding core formed by winding the positive electrode and the negative electrode are subjected to hot pressing, the three-point hardness of the winding core is 80N/0.8-160N/0.8 mm. Compared with the conventional diaphragm and the winding core formed by winding the positive and negative electrodes, the three-point hardness of the winding core after hot pressing is improved by 4-8 times. The conditions of the hot pressing are as described above.
The invention has the beneficial effects that:
the invention provides a coating, and a separator and a battery comprising the coating. The dry bonding force between the coating and the anode is less than or equal to 3N/m before hot pressing, and the coating shows no bonding effect; after hot pressing (hot pressing for 5 s-65 s at 45-100 ℃ and 0.2-0.5 MPa), the coating is changed from a glass state to a high-elastic state, and the dry adhesion force between the coating and the negative electrode is more than 25N/m, and the dry adhesion force between the coating and the positive electrode is more than 30N/m, so that the coating has very strong adhesion. The diaphragm comprising the coating can play a role in fixing the position of the anode and the cathode during winding, and keeps the coverage of the anode and the cathode, so that the specific position of the winding core can be maximally positioned in the packaging process, the accuracy of winding core shell entering is improved, the yield of the winding core in the packaging process is improved, the pole piece folding proportion caused by turnover aging is reduced, the primary pass rate of the battery core can be greatly improved, and the reject rate of products and the reworking rate of the battery core are reduced.
Drawings
Fig. 1: the structure schematic diagram of the three-point hardness testing device for the winding core.
Fig. 2: and a sample preparation diagram for testing dry adhesion between the diaphragms or between the diaphragms and the positive and negative plates.
Fig. 3: schematic diagram of a testing device for dry bonding force between the diaphragms or between the diaphragms and the positive and negative plates.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
In the present invention, the term "three-point hardness of a winding core" refers to the hardness of a bare winding core tested by three-point test on a three-point hardness tester, and the short side is pressed down by a specific distance (for example, 0.8 mm), and is specifically shown in fig. 1.
Fig. 1 is a schematic structural diagram of a testing device for testing three-point hardness of a winding core after the winding core is placed in a stage, and the specific operation process is as follows: hot-pressing the wound core (hot-pressing condition: temperature: 45 ℃, surface pressure: 0.3MPa, duration: 45 s); the hot-pressed winding cores are placed on a three-point hardness tester for testing: short side pressing placement condition: the tab side is faced to a tester, the long side is placed on the cylindrical iron strips on the two sides, the distance between the cylindrical iron strips and the edge is 0.015 times the width of the winding core, and then the winding core is placed in the middle for testing; equipment calibration, zero clearing, and selecting a pressing distance of 0.8mm and a pressing speed: 10mm/min; the maximum force of 0.8mm pressing down is obtained.
Fig. 2 and 3 are schematic diagrams of a test sample and a test apparatus for evaluating dry adhesion between separators or between a separator and positive and negative plates, and the test method is also described in detail in CN202011451375.1, wherein dry peeling force is dry adhesion.
The following is described for specific cell tests: cutting a diaphragm with a fixed width (for example, 15 mm) and positive and negative plates; according to the diaphragm&Diaphragm, diaphragm&Positive electrode or separator&The negative electrode is compounded, and paper or other medium is isolated at the head, so that the subsequent separation is convenient; and then carrying out hot pressing on the prepared sample, wherein the hot pressing conditions are as follows: temperature: 100 ℃, pressure: 0.2MPa, action time: 10s (diaphragm)&Diaphragm) Or 60s (diaphragm)&Positive electrode and separator&Negative electrode) to obtain a sample to be measured; then the prepared sample to be tested is tested and is placed on an electronic universal testing machine to test, and the diaphragm is tested&Dry adhesion of separator, separator&Dry adhesion and separator for positive electrode&Dry adhesion of the negative electrode, test conditions: test unit: n/m, test length: 50mm, test speed: 200mm/min, initial acceleration: 200mm/min 2 。
The following capacity retention and thickness expansion ratios of 1000T cells at 25 ℃ were measured by the following methods:
thickness D of full cell before test 0 Placing the battery in an environment with the temperature of (25+/-3) DEG C, standing for 3 hours, when the battery core body reaches the temperature of (25+/-3), charging the battery to 4.2V according to 1C, charging to 4.4V according to 0.7C, charging to the cut-off current of 0.05C under a constant voltage of 4.4V, discharging to 3V according to 0.5C, and recording the initial capacity Q 0 When the number of times of cycling is required or the capacity decay rate is lower than 70% or the thickness exceeds the thickness required by the test, the previous discharge capacity is taken as the capacity Q of the battery 2 Calculating the capacity retention rate (%), fully electrifying the battery, taking out the battery core, standing for 3 hours at normal temperature, and testing the full-electricity thickness D 2 The thickness change rate (%) was calculated, and the result was recorded. The calculation formula used therein is as follows: thickness change rate (%) = (D) 2 -D 0 )/D 0 X 100%; capacity retention (%) =q 2 /Q 0 ×100％。
The following test process of the packaging yield is:
the number of input winding cores is C, and the number of the complete air bag belt batteries is C1. The calculation formula used therein is as follows: package yield = C1/C x 100%.
Example 1
Positive electrode structure: the foil material is aluminum foil with the thickness of 10 mu m; the positive electrode coating layer includes: the positive electrode active material is LiCoO 2 The mass ratio is 97.80%; the conductive agent is conductive carbon black, and the mass ratio of the conductive agent to the conductive carbon black is 1.10%; the binder is polyvinylidene fluoride, and the mass ratio is 1.10%;
negative electrode structure: the foil material is copper foil with the thickness of 5 mu m; the negative electrode coating layer includes: the negative electrode active material is mesophase carbon microsphere, the mass ratio is 96.50%, the conductive agent is carbon nanotube, the mass ratio is 0.90%, the binder is SBR, the mass ratio is 1.30%, the dispersant is sodium carboxymethylcellulose CMC, the mass ratio is 1.30%;
electrolyte solution: EC: EMC: dec=3:5:2, lipf 6 The mass of the electrolyte accounts for 13 percent of the total mass of the electrolyte.
A diaphragm: the diaphragm comprises a diaphragm substrate and coating layers arranged on the surfaces of two sides of the diaphragm substrate; the coating-forming slurry includes:
methacrylic acid: 10 parts by mass;
acrylamide: 5 parts by mass;
methyl methacrylate: 10 parts by mass;
butyl acrylate: 10 parts by mass;
glycidyl methacrylate: 3 parts by mass;
sodium Dodecyl Benzene Sulfonate (SDBS): 0.3 parts by mass;
dodecylphenol polyoxyethylene ether (OP-10): 0.3 parts by mass;
sodium bicarbonate: 0.01 parts by mass;
ammonia water: 1 part by mass;
hydrogenation of C5 petroleum resin: 5 parts by mass;
hydrogenation of C9 petroleum resin: 5 parts by mass;
ammonium persulfate: 0.06 parts by mass;
deionized water: 50.33 parts by mass.
Preparing slurry according to the proportion to form slurry with the solid content of about 50%, selecting polypropylene as a diaphragm substrate, and then performing transfer coating on two sides of the diaphragm substrate through a micro-concave roller to finish diaphragm coating; coating and controlling according to the sizing agent to obtain the single-sided surface density of 0.2g/m 2 The obtained diaphragm is matched with the positive and negative plates to obtain two groups of battery cells, and the battery is obtained through packaging, liquid injection, formation, secondary sealing, sorting and OCV.
Example 2
Other operations are the same as in example 1, except that: the single-sided surface density is 0.4g/m 2 Is provided.
Example 3:
other operations are the same as in example 1, except that: the single-sided surface density is 0.6g/m 2 Is provided.
Example 4:
other operations are the same as in example 1, except that: the single-sided surface density is 0.8g/m 2 Is provided.
Example 5:
other operations are the same as in example 1, except that: the single-sided surface density is 1.0g/m 2 Is provided.
Comparative example 1:
other operations are the same as in example 1, except that: the composition of the slurries was different:
PVDF accounts for 8%, B9 glue accounts for 3%, dispersant LA133 accounts for 0.3%, nekal BX wetting agent accounts for 0.3%, CMC accounts for 0.8%, and deionized water accounts for 87.6%; the obtained aqueous solution with the solid content of 12.4 percent is coated with a membrane by a micro gravure roll to obtain the membrane with the single-sided surface density of 0.6g/m 2 Is provided.
Comparative example 2:
other operations are the same as in example 3, except that: the coating-forming slurries used do not include methyl methacrylate.
Comparative example 3:
other operations are the same as in example 3, except that: the coating-forming slurries used do not include methacrylic acid.
The separator and the positive and negative electrodes of the above examples and comparative examples were tested, and the test results are as follows:
as can be seen from the above table, the dry press adhesion and three-point hardness of the winding core prepared by the separator of the present invention are clearThe display is enlarged, the shaping effect of the winding core can be achieved, defective products in the packaging process can be reduced, and the primary yield of the packaging process is improved. Moreover, since methyl methacrylate plays a role of a skeleton, the adhesiveness of the separator of comparative example 2 lacking methyl methacrylate is significantly lowered; the coating syrup system of comparative example 3 lacking methacrylic acid was difficult to stabilize and thus could not be coated because methacrylic acid thickened the system. In addition, the battery core prepared by the diaphragm also shows good capacity retention rate and thickness expansion rate in 25 ℃ cycle performance, and the density of the battery core along with the coating surface is 0.6g/m 2 When the battery is in use, the capacity retention rate and the thickness expansion rate of the battery are optimal, and the battery cell capacity retention rate and the battery cell thickness expansion rate can be achieved at the same time under the condition that the packaging once yield is very high, and the surface density reaches 0.8g/m 2 In the above cases, the cells after the dissection cycle find that the cells have a local black spot lithium precipitation phenomenon, which is also a cause of increasing the cell capacity retention rate and the cell thickness expansion rate.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A separator for a battery, the separator comprising a coating comprising the following components: acid monomers, ester monomers, amide monomers, hydrogenated carbon-five petroleum resin, hydrogenated carbon-nine petroleum resin, surfactant, buffer, neutralizer and initiator; the ester monomers include methyl methacrylate, butyl acrylate and glycidyl methacrylate; the acid monomer comprises methacrylic acid;
the coating comprises the following components in parts by mass:
acid monomer: 8-14 parts by mass;
amide monomer: 3-7 parts by mass;
ester monomer: 17-33 parts by mass;
hydrogenated carbon five petroleum resin: 1-9 parts by mass;
hydrogenated carbon nine petroleum resin: 1-9 parts by mass;
and (2) a surfactant: 0.2-1 parts by mass;
buffering agent: 0.005-0.015 parts by mass;
neutralizing agent: 0.5-1.5 parts by mass;
and (3) an initiator: 0.03-0.09 parts by mass;
wherein the ester monomer comprises the following components in parts by mass:
methyl methacrylate: 8-14 parts by mass;
butyl acrylate: 8-14 parts by mass;
glycidyl methacrylate: 1-5 parts by mass;
the surface density of the coating is 0.4-1.0 g/m 2 。
2. The separator of claim 1, wherein the acid-based monomer further comprises at least one of acrylic acid and itaconic acid;
and/or the ester monomer further comprises at least one of ethyl acrylate and isooctyl acrylate;
and/or the amide monomer is at least one selected from acrylamide, methacrylamide and N-methylol acrylamide;
and/or the number average molecular weight of the hydrogenated carbon five petroleum resin is 300-3000; the softening point of the hydrogenated carbon five petroleum resin is 80-130 ℃;
and/or the number average molecular weight of the hydrogenated carbon nine petroleum resin is 300-3000; the softening point of the hydrogenated carbon nine petroleum resin is 90-150 ℃;
and/or the surfactant is at least one selected from Sodium Dodecyl Benzene Sulfonate (SDBS), sodium Dodecyl Sulfate (SDS), dodecylphenol polyoxyethylene ether (OP-10), nonylphenol polyoxyethylene ether sulfate and tween-85;
and/or the buffer is at least one selected from sodium bicarbonate and sodium carbonate;
and/or the neutralizer is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water;
and/or the initiator is at least one selected from ammonium persulfate and sodium persulfate.
3. The separator according to claim 1 or 2, wherein the coating comprises the following components in parts by mass:
methacrylic acid: 8-14 parts by mass;
acrylamide: 3-7 parts by mass;
methyl methacrylate: 8-14 parts by mass;
butyl acrylate: 8-14 parts by mass;
glycidyl methacrylate: 1-5 parts by mass;
sodium Dodecyl Benzene Sulfonate (SDBS) or Sodium Dodecyl Sulfate (SDS): 0.1-0.5 parts by mass;
dodecylphenol polyoxyethylene ether (OP-10): 0.1-0.5 parts by mass;
ammonium persulfate: 0.03-0.09 parts by mass;
sodium bicarbonate: 0.005-0.015 parts by mass;
ammonia water: 0.5-1.5 parts by mass;
hydrogenated carbon five petroleum resin: 1-9 parts by mass;
hydrogenated carbon nine petroleum resin: 1-9 parts by mass.
4. A separator according to claim 1 or 2, wherein the separator comprises a separator substrate and a coating layer provided on at least one side surface of the separator substrate.
5. The membrane of claim 4, further comprising a ceramic layer disposed on a surface of the membrane substrate and/or on a surface of the coating.
6. A battery comprising the separator of any one of claims 1-5.
7. The battery of claim 6, wherein the battery comprises a positive electrode and a negative electrode, and wherein the positive electrode and the negative electrode are separated by the separator; the dry adhesion between the separator and the negative electrode is 25N/m or more, and the dry adhesion between the separator and the positive electrode is 30N/m or more.
8. The battery according to claim 6, wherein the three-point hardness of the winding core formed by winding the separator and the positive electrode is 80-160N/0.8 mm after hot pressing.
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