CN110459773B - Lithium ion battery pole piece slurry, pole piece, preparation method and application thereof - Google Patents
Lithium ion battery pole piece slurry, pole piece, preparation method and application thereof Download PDFInfo
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- CN110459773B CN110459773B CN201910849206.4A CN201910849206A CN110459773B CN 110459773 B CN110459773 B CN 110459773B CN 201910849206 A CN201910849206 A CN 201910849206A CN 110459773 B CN110459773 B CN 110459773B
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- pole piece
- flexibilizer
- slurry
- butanediol
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 86
- 239000002002 slurry Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 58
- 239000011267 electrode slurry Substances 0.000 claims description 56
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 51
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 46
- 229960004063 propylene glycol Drugs 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 29
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 235000013772 propylene glycol Nutrition 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 229940083957 1,2-butanediol Drugs 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000676 Si alloy Inorganic materials 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 31
- 238000012545 processing Methods 0.000 abstract description 17
- 230000002035 prolonged effect Effects 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 10
- 125000003158 alcohol group Chemical group 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 5
- 229940035437 1,3-propanediol Drugs 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229940093476 ethylene glycol Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229960005335 propanol Drugs 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002968 anti-fracture Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000000707 layer-by-layer assembly 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
- 230000003446 memory effect Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium ion battery pole piece slurry, a pole piece, a preparation method and an application thereof, wherein the pole piece slurry comprises the following components: the electrode comprises an electrode active material, a conductive agent, a binder, a solvent and a flexibilizer, wherein the flexibilizer is alcohol with the carbon number of 2-5, the sum of the contents of the solvent and the flexibilizer is 100%, and the volume percentage of the flexibilizer is 0.1-15%; when the pole piece is prepared, the pole piece is prepared by mixing a flexibilizer into pole piece slurry, or the surface of the prepared pole piece is coated with the flexibilizer, so that the pole piece with low hardness and brittleness is obtained; meanwhile, the invention also provides a method for reducing the fracture of the pole piece, which is realized by adding a flexibilizer into the pole piece. The probability of breakage of the positive pole piece in the processing and using processes is greatly reduced, the processing yield and the use safety of the lithium ion battery are improved, the problem that powder falls off in the charging and discharging processes of the negative pole is solved, and the service life of the lithium ion battery is prolonged.
Description
Technical Field
The invention relates to the technical field of power batteries, in particular to lithium ion battery pole piece slurry, a pole piece and a preparation method and application thereof.
Background
Lithium ion batteries have the advantages of no pollution, high energy density and power density, high voltage, long cycle life, small self-discharge, no memory effect and the like, have been widely used in portable electronic devices such as smart phones, notebooks, tablet computers and the like, and have also been widely used as power batteries for vehicles along with the development of electric vehicles. With the popularization of electric vehicles, consumers urgently need a high-energy-density power lithium ion battery to meet the requirements of increasing the endurance mileage and prolonging the service life of the electric vehicles.
Currently, in order to improve the energy density and cycle life of a lithium ion battery, researchers often adopt a technical means of coating and/or doping a positive electrode material. CN101714634A discloses a carbon-coated lithium iron phosphate material, which is prepared by performing microwave heating and vapor phase pyrolysis on a carbon source gas to deposit a carbon species on the surface of lithium iron phosphate, so as to obtain a uniform and firm lithium iron phosphate with a complete carbon-coated structure.
CN108448113A discloses a doped modified lithium iron phosphate cathode material, which is prepared by taking battery-grade lithium carbonate doped with magnesium or magnesium and rare earth as a lithium source, mixing the lithium source with an iron source, a phosphorus source and a carbon source, grinding, drying to obtain a doped modified lithium iron phosphate precursor, and roasting the precursor to obtain a lithium iron phosphate cathode material product with the Mg content of 0.06-1.75%. The lithium iron phosphate anode material prepared by the method realizes uniform doping of magnesium, cerium or lanthanum in lithium iron phosphate, has superior discharge capacity, cycle performance and rate capability, and better meets the application requirements.
CN108807931A discloses a high-nickel material with a surface coated with lithium aluminum silicate and a surface layer doped with fluorine, the high-nickel material comprises a lithium aluminum silicate coating layer and a high-nickel ternary material center layer, the coating layer is 1 nm-200 nm thick and is doped with fluorine, the coating layer of the lithium aluminum silicate fast ion conductor material has good lithium ion conductivity, oxygen in the coating layer or the high-nickel material is replaced by doping of fluorine ions, so that the electronic conductivity of the material is improved, the surface of the high-nickel material is enabled to have good lithium ion and electronic conductivity at the same time, and the multiplying power performance of the lithium ion battery anode material is favorably exerted.
Researchers have adopted technical means such as compounding, coating, oxidation treatment and the like for the negative electrode material. CN108231427A discloses a 3D porous graphene/transition metal oxide composite material and a preparation method and application thereof, wherein the preparation method of the composite material comprises the following steps: dispersing graphite oxide into water by ultrasonic, adding transition metal salt and sodium bicarbonate, stirring and dissolving to obtain a mixed solution; the mixed solution is transferred into a hydrothermal reaction kettle for hydrothermal reaction, a hydrothermal reaction product is dried and then placed in a protective atmosphere for calcination, and the 3D porous graphene/transition metal oxide composite material with a 3D porous structure and the transition metal oxide growing on the surface of the graphene in situ is obtained.
CN104916826A discloses a graphene-coated silicon negative electrode material and a preparation method thereof, the preparation method comprises the following steps: A. preparing a graphene oxide suspension; B. preparing a nano silicon particle suspension; C. and preparing the graphene-coated silicon negative electrode material. The preparation method adopts the electrostatic self-assembly synthesis technology, and has the advantages of wide raw material source, low price, simple synthesis method, easy control of process conditions, strong operability and good repeatability. The graphene-coated silicon negative electrode material disclosed by the invention is high in specific capacity, excellent in cycle performance and rate capability, the first discharge specific capacity reaches 2746mAh/g under the current density of 0.01-1.2V and 200mA/g, and the discharge specific capacity is kept at 803.8mAh/g after 100 cycles.
CN103474642A discloses a tin oxide negative electrode material for lithium ion batteries and a preparation method thereof. The method comprises the steps of firstly electroplating a metallic tin coating on one side of the surface of a pretreated copper strip substrate, wherein the thickness of the metallic tin coating is 10-15 mu m, secondly, carrying out anodic oxidation treatment on the material obtained in the first step to obtain a mesoporous oxide, and then carrying out heat treatment to finally prepare the lithium ion battery cathode material with a mesoporous tin oxide layer attached to one side of the surface of the copper strip substrate, wherein the diameter of a mesoporous is 3-10 nm, and the thickness of the obtained oxide layer is 5-10 mu m. The first discharge specific capacity of the lithium ion negative electrode material prepared by the invention can reach 600mAh/g at most and is about 2 times of that of the conventional carbon material. The preparation process is simple, and the prepared tin oxide-based negative electrode material has excellent performance.
The above documents show that research on electrode materials by researchers is limited to modification of active materials to improve electrochemical properties such as capacity, cycle performance, rate performance, etc., but there is a great difference between laboratory-stage research and industrial production.
The ternary cathode material with higher nickel content and the graphite with higher gram capacity are usually selected in industrial production, and the compaction density of the electrode material is improved so as to improve the capacity and the energy density of the battery. However, the positive electrode is made of a high nickel material and the compacted density of the pole piece is improved, so that the pole piece becomes very fragile and is easy to break in the pole piece processing process, the possibility of breaking the pole piece also exists in the use process of the manufactured battery, and the broken pole piece is likely to puncture a diaphragm to form a short circuit with the negative electrode, so that the safety problem is caused. The volume expansion of the negative electrode material graphite is large when the negative electrode material graphite is charged, and if the compacted density of the pole piece is increased, the problem that the graphite falls off from the surface of the negative electrode current collector in the charging and discharging process of the battery can be caused, the capacity of the pole piece is reduced remarkably, the diaphragm is pierced, and the short circuit is caused, so that the service life of the lithium ion battery is influenced.
Therefore, how to make the battery have a positive electrode plate or a negative electrode plate with good flexibility, the positive electrode plate makes the battery not have the problem of breakage of the electrode plate due to the use of high nickel and high compaction process, and the negative electrode plate does not have the problem of graphite falling due to the use of high gram capacity graphite and the use of high compaction density process, so as to improve the safety and the service life of the battery, which has become a technical problem to be solved urgently at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides lithium ion battery pole piece slurry, a pole piece, and a preparation method and application thereof. By adding the flexibilizer into the pole piece slurry, the problem of pole piece fracture of the positive pole piece due to the use of a high-nickel material and a high-compaction density process is well solved, and the processing yield and the use safety of the positive pole piece are improved; meanwhile, the problem that graphite falls off due to the use of high-gram-capacity graphite and the use of a high-compaction-density process of the negative pole piece is solved, and the service life of the negative pole piece is prolonged. Due to the improvement of the electrode pole piece, the cycle life of the lithium ion battery prepared by the electrode pole piece is correspondingly prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium ion battery electrode plate slurry, including: an electrode active material, a conductive agent, a binder, a solvent, and a flexibilizing agent; the flexibilizer is alcohol with 2-5 carbon atoms; the total content of the solvent and the flexibilizer is 100%, and the volume percentage of the flexibilizer is 0.1-15%.
According to the invention, the electrode plate has good flexibility by adding the flexibilizer into the battery electrode plate slurry. The flexibilizer has the swelling characteristic of an organic solvent to a high polymer material, and can reduce the rigidity of the adhesive after entering between adhesive high polymer chains. Meanwhile, hydroxyl in the flexibilizer can form hydrogen bonds with polar groups which are not acted with the positive and negative electrode materials in the binder, so that the interaction of the polar groups in the binder is reduced, a rigid net structure formed by the rigid net structure is dissociated to a certain degree, the effect of reducing the hard brittleness of the electrode plate is further achieved, the problem of breakage of the positive electrode plate in the processing and using processes is solved, the processing yield and the use safety of the battery are further improved, the problem of graphite falling off of the negative electrode plate in the using process is also solved, and the service life of the negative electrode plate is prolonged. Due to the improvement of the electrode slurry, the cycle life of the lithium ion battery prepared by the electrode slurry is correspondingly improved.
In the present invention, the flexibilizing agent is an alcohol having 2 to 5 carbon atoms, and may be, for example, a monohydric alcohol or a polyhydric alcohol having 2, 3, 4 or 5 carbon atoms, and specifically may be any one or a combination of at least two of ethanol, ethylene glycol, propanol, 2-propanol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, or pentanol.
Preferably, the flexibilizing agent is any one or a combination of at least two of ethylene glycol, propanol, 2-propanol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, preferably any one or a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, more preferably a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, wherein a typical but non-limiting combination is: 1, 2-propanediol and 1, 3-butanediol, 1, 3-butanediol and 1, 4-butanediol, 1, 2-propanediol and 1, 3-butanediol.
In the present invention, the content of the flexibilizing agent is 0.1 to 15% by volume, for example, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.8%, 4%, 4.2%, 5%, 5.6%, 6%, 6.4%, 7%, 7.5%, 8%, 8.2%, 9%, 9.5%, 10%, 10.2%, 11%, 11.5%, 12%, 12.8%, 13%, 13.4%, 14%, 14.7% or 15%, based on 100% of the sum of the contents of the solvent and the flexibilizing agent.
According to the invention, by selecting the type of the flexibilizer and matching the content ratio of the flexibilizer in the pole piece slurry, the flexibilizer can better exert the effect of reducing the hard brittleness of the pole piece, the fracture property of the pole piece is reduced, and the service life of the lithium ion battery is also prolonged.
Preferably, the electrode active material is a positive electrode active material or a negative electrode active material.
Preferably, the positive electrode active material is any one or a combination of at least two of ternary materials, lithium iron phosphate, lithium cobaltate or lithium manganate, wherein the ternary materials include, but are not limited to NCM333, NCM523, NCM613, NCM622, NCM811 or NCA, and typical but non-limiting combinations of the positive electrode active materials are: NCA and lithium iron phosphate, lithium cobaltate and lithium manganate, NCM811, lithium iron phosphate, lithium cobaltate and lithium manganate.
Preferably, the negative active material is any one of lithium titanate, graphite, silicon alloy, silicon oxide or tin alloy or a combination of at least two of them, wherein a typical but non-limiting combination is: lithium titanate and graphite, silicon alloys and graphite, silicon and tin alloys, graphite, oxides of silicon and tin alloys.
Preferably, the conductive agent is any one of carbon black, acetylene black, graphite powder, ketjen black, or carbon fiber, or a combination of at least two thereof, wherein a typical but non-limiting combination is: carbon black and acetylene black, ketjen black and carbon fibers, graphite powder, acetylene black and ketjen black, carbon black, ketjen black, graphite powder and carbon fibers.
Preferably, the binder is any one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, polypropylene alcohol or sodium carboxymethylcellulose, wherein a typical but non-limiting combination is: polytetrafluoroethylene and polyallylic alcohol, styrene butadiene rubber and sodium carboxymethylcellulose, polyallylic alcohol, styrene butadiene rubber and sodium carboxymethylcellulose.
Preferably, the solvent is any one of N-methyl pyrrolidone, distilled water, dimethyl sulfoxide or tetrahydrofuran or a combination of at least two thereof, wherein a typical but non-limiting combination is: n-methylpyrrolidone and tetrahydrofuran, distilled water and tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
In the present invention, the specific types of the electrode active material, the conductive agent, the binder and the solvent used in the electrode sheet slurry are not particularly limited, and any types commonly used by those skilled in the art are suitable for the present invention.
In a second aspect, the present invention provides a lithium ion battery electrode plate, which comprises a current collector and a membrane, wherein the membrane contains the lithium ion battery electrode plate slurry according to the first aspect.
Preferably, the lithium ion battery pole piece is a positive pole piece or a negative pole piece.
The lithium ion battery pole piece provided by the invention comprises the lithium ion battery pole piece slurry in the first aspect, and the electrode pole piece has good flexibility by using the flexibilizer, so that the problem of pole piece fracture caused by the use of a high-nickel material and a high compaction density process of the positive pole piece is solved, the processing yield and the use safety of the positive pole piece are improved, the problems of volume expansion of the negative pole and falling of a negative active substance from a current collector in the charging and discharging process are solved, the service life of the negative pole is prolonged, and the cycle life of the lithium ion battery prepared by the battery pole piece is prolonged.
In a third aspect, the invention provides a method for preparing a lithium ion battery pole piece according to the second aspect, which comprises the following steps:
(1) adding a negative electrode active material, a conductive agent, a binder and a flexibilizer into a solvent according to a proportion, and uniformly mixing to obtain negative electrode slurry;
(2) coating the negative electrode slurry on the surface of a negative electrode current collector, and baking to obtain a negative electrode plate of the lithium ion battery; alternatively, the first and second electrodes may be,
(1') adding a positive electrode active substance, a conductive agent, a binder and a flexibilizer into a solvent in proportion, and uniformly mixing to obtain positive electrode slurry;
(2') coating the positive electrode slurry on the surface of the positive electrode current collector, and baking to obtain the positive electrode piece of the lithium ion battery.
According to the invention, the electrode slurry is obtained by uniformly mixing the flexibilizer, the electrode active material, the conductive agent and the binder, the electrode slurry is coated on the surface of the current collector, and the electrode plate is obtained by baking, so that the electrode plate has good flexibility, the electrode material and the current collector are combined more tightly, the problem that the positive electrode plate is easy to break in the processing and using processes is solved, the processing yield and the safety performance of the positive electrode plate are improved, the interaction between the electrode materials on the negative electrode plate is enhanced, the electrode material is prevented from falling off from the current collector in the charging and discharging processes, and the service life of the negative electrode is prolonged.
In a fourth aspect, the present invention further provides a lithium ion battery electrode plate, including: the flexible agent is coated on the surface of the lithium ion battery pole piece;
the flexibilizer is alcohol with 2-5 carbon atoms, and the coating amount of the flexibilizer is 0.01-1.5% of the weight of the pole piece in the coating area.
According to the invention, the surface of the battery pole piece is coated with the flexible agent, so that the problem of breakage of the positive pole piece in the processing and using processes is solved, the processing yield and the use safety of the battery are improved, the problem of graphite falling off in the using process of the negative pole is also solved, and the service life of the negative pole is prolonged. Due to the improvement of the electrode slurry, the cycle life of the lithium ion battery prepared by the electrode slurry is correspondingly improved.
The flexibilizer is an alcohol with 2-5 carbon atoms, for example, the flexibilizer can be monohydric alcohol or polyhydric alcohol with 2, 3, 4 or 5 carbon atoms, and specifically can be any one or a combination of at least two of ethanol, ethylene glycol, propanol, 2-propanol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol or pentanol.
The coating amount of the flexibilizer is 0.01 to 1.5% of the weight of the electrode sheet in the coating area, and may be, for example, 0.01%, 0.02%, 0.05%, 0.07%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.55%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.4%, or 1.5%.
Preferably, the flexibilizing agent is any one or a combination of at least two of ethylene glycol, propanol, 2-propanol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, preferably any one or a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, further preferably a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, wherein a typical but non-limiting combination is: 1, 2-propanediol and 1, 3-butanediol, 1, 3-butanediol and 1, 4-butanediol, 1, 2-propanediol and 1, 3-butanediol.
In a fifth aspect, the present invention provides a method for preparing a lithium ion battery pole piece according to the fourth aspect, including the following steps:
(a) adding a negative electrode active material, a conductive agent and a binder into a solvent according to a proportion, and uniformly mixing to obtain negative electrode slurry;
(b) coating the negative electrode slurry on the surface of a negative electrode current collector and drying to form a negative electrode piece;
(c) spraying a flexible agent on the surface of the dried negative pole piece, and rolling, die cutting and splitting to prepare the negative pole piece; alternatively, the first and second electrodes may be,
(a') adding a positive active substance, a conductive agent and a binder into a solvent according to a proportion, and uniformly mixing to obtain positive slurry;
(b') coating the positive electrode slurry on the surface of a positive electrode current collector and drying to form a positive electrode plate;
and (c') spraying the flexible agent on the surface of the dried positive plate, and rolling, die cutting and splitting to prepare the positive plate.
According to the invention, the electrode plate with good flexibility is prepared by spraying the flexibilizer on the surface of the electrode plate, so that the probability of breakage of the positive electrode plate in the processing and using processes is reduced, the processing yield and the use safety of the battery are improved, the graphite falling off condition of the negative electrode in the using process is reduced, and the service life of the negative electrode is prolonged. Due to the improvement of the electrode pole piece, the cycle life of the lithium ion battery prepared by the electrode pole piece is correspondingly prolonged.
In a sixth aspect, the invention also provides a method for reducing the fracture property of the pole piece, and the method adopts the addition of a flexibilizer in the pole piece.
According to the invention, the flexibilizer is added into the pole piece, the flexibilizer has the swelling characteristic of the organic solvent to the high polymer material, and the rigidity of the adhesive can be reduced after the flexibilizer enters between the high polymer chains of the adhesive. Meanwhile, hydroxyl in the flexibilizer can form hydrogen bonds with polar groups which are not acted with the positive and negative electrode materials in the binder, so that the interaction of the polar groups in the binder is reduced, a rigid net structure formed by the rigid net structure is dissociated to a certain degree, and the effect of reducing the hard brittleness of the electrode plate is further achieved, so that the mechanical property and the tensile strength of the electrode plate are improved, the problem of breakage of the positive electrode plate in the processing and using processes is solved, the processing yield and the use safety of the battery are improved, the problem of graphite falling off of the negative electrode in the using process is also solved, and the service life of the negative electrode is prolonged. Due to the improvement of the electrode pole piece, the cycle life of the lithium ion battery prepared by the electrode pole piece is correspondingly prolonged.
Preferably, the flexibilizing agent is an alcohol with 2-5 carbon atoms, preferably any one or a combination of at least two of ethylene glycol, propanol, 2-propanol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol, more preferably any one or a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol, more preferably a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol, wherein a typical but non-limiting combination is as follows: 1, 2-propanediol and 1, 3-butanediol, 1, 3-butanediol and 1, 4-butanediol, 1, 2-propanediol and 1, 3-butanediol.
Preferably, in the method for reducing the fracture of the pole piece, the pole piece is prepared by adding the flexibilizer into pole piece slurry; the method comprises the following steps of calculating by taking the sum of the contents of a solvent and a flexibilizer in the pole piece slurry as 100%, wherein the volume percentage content of the flexibilizer is 0.1-15%;
or coating the flexibilizer on the surface of the pole piece; the coating amount of the flexibilizer is 0.01-1.5% of the weight of the pole piece in the coating area.
Preferably, the pole piece is a positive pole piece or a negative pole piece.
The invention not only provides a method for reducing the fracture or hard brittleness of the positive electrode or the negative electrode piece, but also provides a method for preventing the powder of the negative electrode from falling off in the charging and discharging process, which are realized by adopting the specific operation.
In the invention, the flexibilizer can be added into the positive electrode material and the negative electrode material at the stage of mixing the positive electrode material and the negative electrode material, and can also be added in any one or more processes before coating or rolling of the positive electrode piece and the negative electrode piece or hot pressing and shaping of a bare cell, so that the effects can be realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the electrode slurry provided by the invention, through the introduction of the flexibilizer, the flexibilizer has the swelling characteristic of an organic solvent to a high polymer material, and the rigidity of the binder can be reduced after the flexibilizer enters between the binder high polymer chains; meanwhile, hydroxyl in the flexibilizer can form hydrogen bonds with polar groups which are not acted with the positive and negative electrode materials in the adhesive, so that the interaction of the polar groups in the adhesive is reduced, and a rigid net structure formed by the polar groups is dissociated to a certain degree, so that the effect of reducing the hard brittleness of the pole piece can be achieved, and the pole piece has good flexibility;
(2) according to the positive pole piece provided by the invention, the electrode material and the current collector are combined more tightly by introducing the flexibilizer, so that the problem that the positive pole piece is easy to break in the processing and using processes is solved, and the processing yield and the safety performance of the positive pole piece are improved;
(3) according to the negative pole piece provided by the invention, the interaction between the electrode materials on the negative pole piece is enhanced through the introduction of the flexibilizer, the problem that negative pole powder falls off in the using process is solved, and the service life of the battery is further prolonged;
(4) according to the electrode plate provided by the invention, the anti-fracture performance of the electrode plate is improved by adding the flexibilizer, and the problem of falling off of electrode powder in the use process is solved, so that the cycle life of the lithium ion battery prepared by the electrode plate is 2.5 times of that of the lithium ion battery without the flexibilizer.
Drawings
Fig. 1 is a comparison result of cell capacity retention rates of example 2 and comparative example 2 provided by the present invention.
Detailed Description
The following further describes the technical means of the present invention to achieve the predetermined technical effects by means of embodiments with reference to the accompanying drawings, and the embodiments of the present invention are described in detail as follows.
Preparation example 1
A preparation method of lithium ion battery positive pole piece slurry comprises the following steps:
taking a ternary material (NCM) as a positive electrode active material, carbon black (SP) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, N-methylpyrrolidone (NMP) as a solvent, and mixing a flexibilizer 1, 2-propylene glycol according to a solid weight ratio of NCM: SP: PVDF 98:1:1, and a slurry solid content of 78%, wherein NMP:1, 2-propylene glycol is 98:2 (volume ratio); and then the materials are stirred and mixed evenly at the temperature of 30 ℃ to obtain the anode slurry.
Preparation example 2
A preparation method of lithium ion battery negative pole piece slurry comprises the following steps:
graphite (AG) is used as a negative electrode active substance, Styrene Butadiene Rubber (SBR) is used as a binder, carboxymethyl cellulose (CMC) is used as a dispersing agent, carbon black (SP) is used as a conductive agent, distilled water is used as a solvent, 1, 2-propylene glycol is used as a flexibilizer, and the raw materials are uniformly stirred and mixed according to the proportion AG: SBR: CMC: SP of 96:1.5:1:1.5 to form negative electrode slurry, wherein the solid content of the slurry is 50%, and the weight ratio of the distilled water to the 1, 2-propylene glycol is 99:1 (volume ratio); and then the materials are stirred and mixed evenly at the temperature of 30 ℃ to obtain the cathode slurry.
Preparation example 3
Compared with the preparation example 1, only the flexibilizing agent is replaced by 1, 2-propanediol by 1, 2-butanediol.
Preparation example 4
Compared with preparation example 1, only the flexibilizing agent is replaced by 1, 2-propanediol and 1, 2-butanediol with the volume ratio of 1:1.
Preparation example 5
Compared with the preparation example 1, only the flexibilizing agent is replaced by the ethylene glycol from the 1, 2-propylene glycol.
Preparation example 6
Compared with the preparation example 1, only the flexibilizing agent is replaced by 1, 2-propanediol to 1, 4-butanediol.
Preparation example 7
Compared with preparation example 1, only the content of NMP, the solvent of which, and the flexibilizing agent 1, 2-propanediol, was replaced by NMP:1, 2-propanediol (volume ratio) 99: 1.
Preparation example 8
Compared with preparation example 1, only the content of NMP, the solvent, and 1, 2-propanediol, of the flexibilizing agent was replaced with NMP:1, 2-propanediol (volume ratio) 92: 8.
Preparation example 9
Compared with preparation example 1, only the content of NMP, the solvent, and 1, 2-propanediol, of the flexibilizing agent was replaced with NMP:1, 2-propanediol (volume ratio) 85: 15.
Example 1
A preparation method of a lithium ion battery comprises the following steps:
(1) continuously coating the positive electrode slurry obtained in the preparation example 1 on two sides of an aluminum foil of a positive electrode current collector, and drying, rolling, die-cutting and slitting the coated membrane to prepare a positive electrode plate;
(2) taking graphite (AG) as a negative electrode active substance, carbon black (SP) as a conductive agent, Styrene Butadiene Rubber (SBR) as a binder, distilled water as a solvent and carboxymethyl cellulose (CMC) as a dispersing agent, uniformly stirring and mixing the raw materials according to the solid weight ratio of AG: SBR: CMC: SP 96:1.5:1.5:1 to form negative electrode slurry, wherein the solid content of the slurry is 55%, coating the negative electrode slurry on two sides of a negative electrode current collector copper foil, and preparing a negative electrode pole piece through drying, rolling, die cutting and strip dividing;
(3) and (3) preparing the positive pole piece, the negative pole piece and the isolating membrane according to the following steps: coiling the anode-diaphragm-cathode-diaphragm into a naked electric core by winding;
(4) and (3) assembling and welding the wound naked electric core with the top cover shell after hot pressing to complete electric core assembly, and finally, completing electric core manufacturing of the electric core through processes of liquid injection, formation, exhaust, sealing and the like.
Example 2
A preparation method of a lithium ion battery comprises the following steps:
(1) taking a ternary material (NCM) as a positive electrode active material, carbon black (SP) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a solvent, mixing the materials according to the proportion of NCM: SP: PVDF: 97:1.5:1.5, stirring and uniformly mixing to form positive electrode slurry, wherein the solid content of the slurry is 75%, continuously coating the positive electrode slurry on two surfaces of an aluminum foil of a positive electrode current collector, and drying, rolling, die cutting and striping the coated membrane to prepare a positive electrode piece;
(2) continuously coating the negative electrode slurry obtained in the preparation example 2 on two surfaces of a copper foil of a negative electrode current collector, and preparing a negative electrode plate through drying, rolling, die cutting and stripping;
(3) and (3) preparing the positive pole piece, the negative pole piece and the isolating membrane according to the following steps: coiling the anode-diaphragm-cathode-diaphragm into a naked electric core by winding;
(4) and (3) assembling and welding the wound naked electric core with the top cover shell after hot pressing to complete electric core assembly, and finally, completing electric core manufacturing of the electric core through processes of liquid injection, formation, exhaust, sealing and the like.
Example 3
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 3, as compared with example 1.
Example 4
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 4, as compared with example 1.
Example 5
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 5, as compared with example 1.
Example 6
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 6, as compared with example 1.
Example 7
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 7, as compared with example 1.
Example 8
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 8, as compared with example 1.
Example 9
The same procedure as in example 1 was repeated, except that the positive electrode slurry obtained in production example 1 in step (1) was replaced with the positive electrode slurry obtained in production example 9, as compared with example 1.
Example 10
A preparation method of a lithium ion battery comprises the following steps:
(1) taking a ternary material (NCM) as a positive electrode active material, carbon black (SP) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, N-methylpyrrolidone (NMP) as a solvent, uniformly stirring and mixing the materials according to the solid weight ratio of NCM to SP to PVDF of 96 to 2.5 to 1.5 to form positive electrode slurry, wherein the solid content of the slurry is 70%, continuously coating the positive electrode slurry on two sides of an aluminum foil of a positive electrode current collector, and drying;
(2) spraying 1, 2-propylene glycol on the surface of the dried positive electrode, wherein the spraying amount per unit area is 0.2% of the weight of the positive electrode piece in the area, and preparing the positive electrode piece sprayed with the 1, 2-propylene glycol by rolling, die cutting and stripping;
(3) taking graphite (AG) as a negative electrode active substance, Styrene Butadiene Rubber (SBR) as a binder, carboxymethyl cellulose (CMC) as a dispersant, carbon black (SP) as a conductive agent, and distilled water as a solvent, uniformly stirring and mixing the raw materials according to the solid weight ratio of AG: SBR: CMC: SP (95: 1.5:1.5: 2) to form negative electrode slurry, wherein the solid content of the slurry is 48%, coating the negative electrode slurry on two sides of a negative electrode current collector copper foil, and preparing a negative electrode pole piece through drying, rolling, die cutting and strip dividing;
(4) the positive pole piece and the negative pole piece prepared by the process and the isolating film are prepared according to the following steps: winding the anode-cathode-anode-diaphragm into a bare cell by winding, assembling the wound bare cell with a top cover shell after hot pressing and welding to complete cell assembly, and finally completing cell manufacturing by processes of liquid injection, formation, exhaust, sealing and the like.
Example 11
The same procedure as in example 10 was repeated, except that the amount of 1, 2-propanediol sprayed on the surface of the positive electrode in step (2) was changed to 0.01%, as compared with example 10.
Example 12
The same procedure as in example 10 was repeated, except that the amount of 1, 2-propanediol sprayed on the surface of the positive electrode in step (2) was changed to 1.2%, as compared with example 10.
Comparative example 1
Compared with example 1, the difference is only that the flexibilizer 1, 2-propylene glycol is not mixed in the positive electrode slurry in step (1), and the positive electrode slurry is prepared by the following method:
taking a ternary material (NCM) as a positive electrode active material, carbon black (SP) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, N-methylpyrrolidone (NMP) as a solvent, and stirring and mixing the materials uniformly at the temperature of 30 ℃ to obtain positive electrode slurry, wherein the weight ratio of NCM to SP to PVDF is 98:1:1, and the solid content of the slurry is 78%.
Comparative example 2
Compared with the embodiment 2, the difference is that the anode slurry in the step (2) is not mixed with the flexibilizer 1, 2-propylene glycol, and the anode slurry is prepared by the following method:
graphite (AG) is used as a negative electrode active substance, Styrene Butadiene Rubber (SBR) is used as a binder, carboxymethyl cellulose (CMC) is used as a dispersant, carbon black (SP) is used as a conductive agent, distilled water is used as a solvent, the raw materials are uniformly stirred and mixed according to the solid weight ratio of AG: SBR: CMC: SP 96:1.5:1:1.5 to form negative electrode slurry, the solid content of the slurry is 50%, and the raw materials are uniformly stirred and mixed at the temperature of 30 ℃ to obtain the negative electrode slurry.
Comparative example 3
Compared with the embodiment 10, the difference is that the flexibilizer 1, 2-propylene glycol is not sprayed on the surface of the positive electrode in the step (2).
Evaluation of the breakage of the positive electrode piece:
respectively comparing examples 1 and 10 with comparative examples 1 and 3, adopting a sampling inspection method to count the number of the broken positive pole pieces after each hundred of bare cells are hot-pressed, and repeating the test results for 7 times as follows:
TABLE 1
As can be seen from table 1, compared with comparative example 1, in example 1, after the flexibilizer is added to the positive electrode sheet slurry, the number of the positive electrode sheets broken after each hundred bare cells are hot-pressed is 0, that is, the situation of the sheet breakage does not occur, while in comparative example 1, because the flexibilizer component is not added to the positive electrode sheet slurry, the number of the positive electrode sheets broken can reach 19 at most, and the breakage probability is 3% to 19%.
TABLE 2
As can be seen from table 2, compared with comparative example 3, in example 10, after the surface of the positive electrode sheet is coated with the flexibilizer, the number of the positive electrode sheet broken after each hundred bare cells are hot-pressed is 1-4, while in comparative example 3, because the surface of the positive electrode sheet is not coated with the flexibilizer, the number of the broken positive electrode sheet can reach 16 at most, and the breakage probability is 4-16%.
It can also be seen from the comparison between table 1 and table 2 that when the positive electrode plate is made by adding the flexibilizer to the positive electrode slurry, the fracture resistance is stronger than that when the flexibilizer is coated on the surface of the positive electrode plate.
Comparing the example 2 with the comparative example 2, it is further found that the capacity retention rate of the lithium ion battery cell in the example 2 can reach more than 92% when the lithium ion battery cell is cycled for 1000 cycles by adding the flexibilizer into the negative electrode plate, while the capacity retention rate of the lithium ion battery cell in the comparative example 2 is only 80% when the lithium ion battery cell is cycled for 992 cycles by not adding the flexibilizer into the negative electrode plate, which is obviously lower than the capacity retention rate of the lithium ion battery cell in the example 2, and the specific comparison result is shown in fig. 1.
Evaluation of the powder falling condition of the negative pole piece:
the negative electrode piece obtained in the above example 2 and the negative electrode piece prepared in the comparative example 2 were subjected to a test of the powder falling-off condition, and the test method was:
and after the negative pole piece is rolled, measuring the peeling strength of the negative pole diaphragm powder by using a tensile machine.
The test results are shown in table 3 below:
TABLE 3
| Example 2 | Comparative example 2 | |
| Peel strength N/m | 5.4 | 3.5 |
As can be seen from table 3, in comparison with comparative example 2, in example 2, the peel strength of the negative electrode film powder was 5.4N/m by using the method of mixing the flexibilizer into the negative electrode slurry, while in comparative example 2, the peel strength of the negative electrode film powder was 3.5N/m because the flexibilizer was not mixed into the negative electrode slurry, which is significantly lower than the peel strength of the negative electrode film in example 2, indicating that the problem of the falling-off of the negative electrode powder can be effectively improved by mixing the flexibilizer into the negative electrode slurry.
Evaluation of lithium ion battery capacity, energy density and cycle life:
the lithium ion batteries obtained in the above examples 1 to 12 and the lithium ion batteries prepared in the comparative examples 1 to 3 were subjected to capacity, energy density and cycle life tests, and the test method was as follows:
and (3) testing temperature: 25 ℃ plus or minus 2 DEG C
Testing multiplying power: 1C/1C
The test results are shown in tables 4-5.
TABLE 4
TABLE 5
As can be seen from tables 4 and 5, after the electrode plates are mixed with the flexibilizer in examples 1 to 12, the capacity and the energy density of the lithium ion battery are basically the same as those of the lithium ion battery in comparative examples 1 to 3, wherein the capacity and the energy density of the lithium ion battery are between 101 and 104Ah and between 215 and 222 Wh/kg.
The cycle life of the lithium ion batteries prepared in the examples 1 to 12 is 1314-2490 times, and the cycle life of the lithium ion batteries prepared in the comparative examples 1 to 3 is 992-1029, wherein the cycle life of the lithium ion battery prepared in the example 1 is 2.37 times of that of the lithium ion battery prepared in the comparative example 1, the cycle life of the lithium ion battery prepared in the example 2 is 2.51 times of that of the lithium ion battery prepared in the comparative example 2, and the cycle life of the lithium ion battery prepared in the example 7 is 1.30 times of that of the lithium ion battery prepared in the comparative example 3, and as can be seen by comparison, compared with the comparative examples 1 to 3, the cycle life of the lithium ion battery is remarkably prolonged after the electrode plate of the lithium ion batteries prepared in the examples 1 to 12 is mixed with the flexibilizer; the cycle life of the lithium ion battery prepared in example 1 is 1.81 times of that of the lithium ion battery prepared in example 7, and the comparison shows that when the lithium ion battery prepared by adding the flexibilizer into the positive electrode slurry is adopted, the cycle life is prolonged by 80.89% compared with the lithium ion battery prepared by coating the flexibilizer on the surface of the positive electrode plate; compared with example 1, the cycle life of the lithium ion batteries prepared in examples 7 to 9 is lower than that of the lithium ion battery prepared in example 1, which indicates that the addition amount of the flexibilizer in the slurry is in an optimal range; the cycle life of the lithium ion battery prepared in example 10 is longer than that of the lithium ion battery prepared in example 11, but shorter than that of the lithium ion battery prepared in example 12, and the comparison shows that the coating amount of the flexibilizer on the surface of the positive electrode plate is in an optimal range.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (20)
1. A lithium ion battery pole piece slurry is characterized by comprising:
an electrode active material, a conductive agent, a binder, a solvent, and a flexibilizing agent;
the flexibilizer is any one or the combination of at least two of ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol;
the total content of the solvent and the flexibilizer is 100%, and the volume percentage of the flexibilizer is 2-15%.
2. The pole piece slurry of claim 1, wherein the flexibilizing agent is any one of 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, or 1, 4-butylene glycol, or a combination of at least two thereof.
3. The pole piece slurry of claim 2, wherein the flexibilizing agent is a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol.
4. The pole piece slurry of claim 1, wherein the electrode active material is a positive electrode active material or a negative electrode active material.
5. The pole piece slurry of claim 4, wherein the positive active material is any one of a ternary material, lithium iron phosphate, lithium cobaltate or lithium manganate or a combination of at least two of the above materials.
6. The pole piece slurry of claim 4, wherein the negative active material is any one or a combination of at least two of lithium titanate, graphite, silicon alloy, silicon oxide, or tin alloy.
7. The pole piece slurry of claim 1, wherein the conductive agent is any one of carbon black, acetylene black, graphite powder, Ketjen black, or carbon fiber or a combination of at least two of the foregoing.
8. The pole piece slurry of claim 1, wherein the binder is any one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, polypropylene alcohol or sodium carboxymethylcellulose.
9. The pole piece slurry of claim 1, wherein the solvent is any one or a combination of at least two of N-methyl pyrrolidone, distilled water, dimethyl sulfoxide or tetrahydrofuran.
10. A lithium ion battery pole piece, comprising: a current collector and a diaphragm;
the membrane contains the lithium ion battery pole piece slurry as defined in any one of claims 1 to 9.
11. The lithium ion battery pole piece of claim 10, wherein the lithium ion battery pole piece is a positive pole piece or a negative pole piece.
12. The preparation method of the lithium ion battery pole piece according to claim 10, comprising the following steps:
(1) adding a negative electrode active material, a conductive agent, a binder and a flexibilizer into a solvent according to a proportion, and uniformly mixing to obtain negative electrode slurry;
(2) coating the negative electrode slurry on the surface of a negative electrode current collector, and baking to obtain a negative electrode plate of the lithium ion battery; alternatively, the first and second electrodes may be,
(1') adding a positive active substance, a conductive agent, a binder and a flexibilizer into a solvent according to a proportion, and uniformly mixing to obtain positive slurry;
(2') coating the positive electrode slurry on the surface of a positive electrode current collector, and baking to obtain the positive electrode piece of the lithium ion battery.
13. A lithium ion battery pole piece, comprising: the flexible agent is coated on the surface of the lithium ion battery pole piece;
the flexibilizer is any one or a combination of at least two of ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol, and the coating amount of the flexibilizer is 0.01-1.5% of the weight of the pole piece in the coating area.
14. The lithium ion battery pole piece of claim 13, wherein the flexibilizing agent is any one of 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, or 1, 4-butylene glycol, or a combination of at least two thereof.
15. The lithium ion battery pole piece of claim 14, wherein the flexibilizing agent is a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol.
16. The method for preparing the lithium ion battery pole piece according to claim 13, wherein the method comprises the following steps:
(a) adding a negative electrode active material, a conductive agent and a binder into a solvent according to a proportion, and uniformly mixing to obtain negative electrode slurry;
(b) coating the negative electrode slurry on the surface of a negative electrode current collector and drying to form a negative electrode piece;
(c) spraying a flexible agent on the surface of the dried negative pole piece, and rolling, die cutting and splitting to prepare the negative pole piece; alternatively, the first and second electrodes may be,
(a') adding a positive electrode active substance, a conductive agent and a binder into a solvent according to a proportion, and uniformly mixing to obtain positive electrode slurry;
(b') coating the positive electrode slurry on the surface of a positive electrode current collector and drying to form a positive electrode plate;
and (c') spraying the flexible agent on the surface of the dried positive plate, and rolling, die cutting and splitting to prepare the positive plate.
17. A method for reducing the fracture property of a pole piece is characterized in that a flexibilizer is added into the pole piece;
the flexibilizer is any one or the combination of at least two of ethylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol;
adding the flexibilizer into the pole piece slurry to prepare a pole piece; calculating by taking the sum of the contents of the solvent and the flexibilizer in the pole piece slurry as 100%, wherein the volume percentage of the flexibilizer is 2-15%;
or coating the flexibilizer on the surface of the pole piece; the coating amount of the flexibilizer is 0.01-1.5% of the weight of the pole piece in the coating area.
18. The method of claim 17, wherein the flexibilizing agent is any one of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol, or a combination of at least two thereof.
19. The method of claim 18, wherein the flexibilizing agent is a combination of at least two of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, or 1, 4-butanediol.
20. The method of claim 17, wherein the pole piece is a positive pole piece or a negative pole piece.
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| CN112151756A (en) * | 2020-09-14 | 2020-12-29 | 江苏塔菲尔新能源科技股份有限公司 | Negative plate and battery |
| CN112436146B (en) * | 2020-11-20 | 2022-06-17 | 安徽南都华拓新能源科技有限公司 | Lithium battery positive electrode material, preparation method and lithium battery |
| CN112652801B (en) * | 2020-12-23 | 2022-03-18 | 深圳市言九电子科技有限公司 | Button battery roll core, preparation method thereof and button battery using same |
| CN114976004B (en) * | 2022-05-24 | 2023-08-11 | 苏州清陶新能源科技有限公司 | Negative electrode slurry, negative electrode plate, lithium ion battery and preparation method of lithium ion battery |
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