CN117832397A - Positive plate and preparation method thereof, and secondary battery - Google Patents
Positive plate and preparation method thereof, and secondary battery Download PDFInfo
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- CN117832397A CN117832397A CN202311717453.1A CN202311717453A CN117832397A CN 117832397 A CN117832397 A CN 117832397A CN 202311717453 A CN202311717453 A CN 202311717453A CN 117832397 A CN117832397 A CN 117832397A
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- positive electrode
- active material
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- 238000002360 preparation method Methods 0.000 title description 26
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011267 electrode slurry Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- -1 taurine compound Chemical class 0.000 claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims description 47
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000447 polyanionic polymer Polymers 0.000 claims description 4
- 239000013225 prussian blue Substances 0.000 claims description 4
- 229960003351 prussian blue Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000000278 alkyl amino alkyl group Chemical group 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 27
- 229960003080 taurine Drugs 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 8
- 238000004537 pulping Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 12
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019398 NaPF6 Inorganic materials 0.000 description 2
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Secondary Cells (AREA)
Abstract
The invention discloses a positive plate, which comprises a current collector and an active material layer attached to at least one surface of the current collector, wherein the active material layer comprises taurine compounds A. According to the invention, the taurine compound is added in the positive electrode pulping process, so that the technical problems of unstable viscosity, easy occurrence of slurry gel, poor slurry fluidity and unstable corresponding battery cell performance of the existing high-alkaline positive electrode slurry are solved.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a positive plate, a preparation method thereof and a secondary battery.
Background
In recent years, with the rapid development of new energy automobiles and energy storage batteries in China, the demand for lithium ion batteries is rapidly increased, the demand for upstream raw materials is rapidly increased, the price of raw materials such as lithium carbonate is continuously increased, and the cost of the batteries is continuously high due to the relative delay of the development of lithium ores and the resource singularity of the lithium ores.
The working principle of the sodium ion battery is similar to that of the lithium ion battery, and the sodium ion battery and the lithium ion battery have advantages and disadvantages, and the lithium ion battery and the sodium ion battery coexist in the fields of new energy power batteries and energy storage batteries for a long time in the future and are mutually complemented. Currently, positive electrode materials adopted by sodium ion batteries mainly comprise layered oxides, polyanion positive electrode materials, prussian blue materials and the like. The positive electrode material of sodium ion battery, especially the positive electrode of layered oxide, is easy to be combined with CO in air 2 、H 2 O reacts to form NaOH and Na on the surface of the material 2 CO 3 The content of residual alkali on the surface is high, and the alkaline is stronger than that of a ternary positive electrode used for a traditional lithium ion battery. In a process system adopting PVDF as a binder, residual alkali on the surface of the positive electrode material can attack C-F of the PVDF, dehydrogenation is carried out to form double bonds and a crosslinking reaction is carried out, so that a gel state is generated, agglomeration of positive electrode particles is caused, coating is difficult, and quality and performance of a battery are further affected. This phenomenon is common in ternary material systems in the lithium battery field, especially high nickel paste systems.
In order to neutralize the residual alkali on the surface of the positive electrode material, acid is generally used for neutralization. For example, in the field of lithium ion battery industry, adding a certain amount of oxalic acid in the preparation process of high-nickel NCA slurry can prevent the slurry from becoming colloid to a certain extent. This is already a well known method in the industry, but since oxalic acid is easily decomposed and unstable, its residue in the battery affects the battery performance. In one chinese patent with patent number CN201910195420.2, an organic weak acid such as acetic acid and citric acid is added to the high-nickel ternary positive electrode slurry to solve the problem of water absorption and jelly-like effect in the process of homogenizing the high-nickel ternary material, so as to improve the processing performance, but the residual organic matters are also unstable and are easy to decompose, thus influencing the battery performance. In one chinese patent with patent number CN202310059512.4, a high molecular polymer containing carboxyl (-COOH) is used as one of the binders, and the alkaline substance in the system is neutralized by part of carboxyl, so as to ensure the fluidity of the slurry, and help to promote the uniformity of slurry coating, thereby obtaining a uniform positive plate of sodium ion battery. By adding the acidic polymer, only the gelation time of the slurry is prolonged, and the effect is not obvious.
Thus, the above-described overbased positive electrode material homogenization process still requires further optimization.
Disclosure of Invention
The invention aims to provide a positive plate and a preparation method thereof, and a secondary battery is prepared by adding taurine compounds in the process of positive electrode pulping so as to solve the technical problems of unstable viscosity, easy occurrence of slurry gel, poor slurry fluidity and unstable corresponding battery cell performance of the existing high-alkaline positive electrode slurry.
In order to achieve the above purpose, the following technical scheme is adopted:
the positive plate comprises a current collector and an active material layer attached to at least one surface of the current collector, wherein the active material layer comprises taurine compounds A, and the structural formula of the active material layer is as follows:
wherein R1 and R2 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, alkylaminoalkyl and halogen; r3 and R4 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl and aralkyl.
Further, the R1 and R2 are selected from hydrogen; and R3 and R4 are selected from any one or more of hydrogen, alkyl and aralkyl.
Further, the active material layer further includes at least a positive electrode active material, a conductive agent, and a binder.
Further, the positive electrode active material includes a positive electrode material containing lithium or a positive electrode material containing sodium.
Further, the positive electrode active material includes any one or more of the following materials: lithium cobalt composite oxide and its modified matter, lithium manganese composite oxide and its modified matter, lithium nickel composite oxide and its modified matter, lithium iron phosphate composite oxide and its modified matter, lithium manganese phosphate composite oxide and its modified matter, lithium vanadium phosphate composite oxide and its modified matter, multi-element transition metal lithium oxide and its modified matter, and lithium-rich manganese multi-element transition metal lithium oxide and its modified matter.
Further, the positive electrode active material includes any one or more of the following materials: layered oxide positive electrode material, polyanion positive electrode material, prussian white positive electrode material, and Prussian blue positive electrode material.
Further, the content of the compound a is 0.02% to 1% of the total weight of the active material layer.
The preparation method of the positive plate is at least used for preparing the positive plate and comprises the following steps:
mixing an anode active material, a conductive agent, a binder and a compound A, adding a solvent, and uniformly stirring to obtain electrode slurry;
and (3) after the viscosity of the electrode slurry is regulated, coating the electrode slurry on a current collector, and drying to obtain the battery positive plate.
Further, the compound A is 0.02% -1% of the total mass of the dry powder in the electrode slurry, wherein the total mass of the dry powder is the sum of the mass of the positive electrode active material, the binder, the conductive agent and the compound A.
The secondary battery comprises a negative plate, a diaphragm, electrolyte and a battery shell, and further comprises the positive plate.
By adopting the scheme, the invention has the beneficial effects that:
1) According to the invention, the taurine compound is added into the high-alkalinity positive electrode material, and in the pulping process, as the sulfonic acid in the taurine compound belongs to a medium strong acid, the alkaline group in the system can be neutralized, so that the fluidity and the stability of the slurry are greatly improved, and the slurry gel phenomenon is avoided;
2) After neutralization of the acid group sulfonic acid group in compound A, the corresponding alkali metal sulfonate (-SO) is formed 3 Na，SO 3 Li), ion migration channels are increased, and the ion conduction capacity of the lithium ion battery is higher than that of alkali metal carboxylate, so that the battery multiplying power is improved;
3) The taurine compound also contains NR alkaline groups, and the groups can neutralize acidic substances generated in the battery, such as HF and oxidation products R-H containing active hydrogen, so that corrosion of acid radicals to the positive electrode material is reduced, stability of the positive electrode material is improved, and service life of the battery is prolonged.
Drawings
FIG. 1 is a graph showing the viscosity of the slurry with time in examples 1 to 4 and comparative examples 1 to 4 according to the present invention;
fig. 2 is a cycle chart of lithium ion secondary batteries in examples 1, 3 and comparative examples 1, 3 according to the present invention;
fig. 3 is a graph showing the cycle of the sodium ion secondary battery in examples 2 and 4 and comparative examples 2 and 4 according to the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the specific embodiments.
Referring to fig. 1 to 3, in one embodiment, the present invention provides a positive electrode sheet, including a current collector, and an active material layer attached to at least one surface of the current collector, wherein the active material layer includes a taurine compound a, and has a structural formula:
wherein R1 and R2 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, alkylaminoalkyl and halogen; r3 and R4 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl and aralkyl.
Among them, the current collector is not particularly limited, and may be various positive current collectors known to those skilled in the art such as aluminum foil, carbon coated aluminum foil, composite aluminum foil, etc.; said R1 and R2 are preferably hydrogen; the R3 and R4 are preferably any one or more of hydrogen, alkyl and aralkyl.
In addition, the active material layer includes at least a positive electrode active material, a conductive agent, and a binder.
Wherein the positive electrode active material may include a positive electrode material containing lithium, any one or more of the following materials may be used: lithium cobalt composite oxide and its modified matter, lithium manganese composite oxide and its modified matter, lithium nickel composite oxide and its modified matter, lithium iron phosphate composite oxide and its modified matter, lithium manganese phosphate composite oxide and its modified matter, lithium vanadium phosphate composite oxide and its modified matter, multi-element transition metal lithium oxide and its modified matter, and lithium-rich manganese multi-element transition metal lithium oxide and its modified matter.
Meanwhile, the positive electrode active material may also include a positive electrode material containing sodium, which may employ any one or more of the following materials: layered oxide positive electrode material, polyanion positive electrode material, prussian white positive electrode material, and Prussian blue positive electrode material.
In addition, in the present invention, the conductive agent is not particularly limited, and may be a positive electrode conductive agent conventional in the art, and may include one or more of acetylene black, conductive carbon black, conductive graphite, carbon fiber, carbon nanotube, and graphene.
And the present invention is not particularly limited as well, and may be known to those skilled in the art, for example, one or more of fluorine-containing resins and polyolefin compounds such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose type binders, rubber type binders such as styrene-butadiene rubber (SBR), polyacrylate type binders, and polyimide.
Further, in a preferred embodiment, the content of the compound a is 0.02% to 1% of the total weight of the active material layer.
In another embodiment, a method for preparing a positive electrode sheet is provided, which is at least used for preparing the positive electrode sheet, and includes the following steps:
mixing an anode active material, a conductive agent, a binder and a compound A, adding a solvent, and uniformly stirring to obtain electrode slurry;
and (3) after the viscosity of the electrode slurry is regulated, coating the electrode slurry on a current collector, and drying to obtain the battery positive plate.
Wherein the compound A is 0.02-1% of the total mass of the dry powder in the electrode slurry, and the total mass of the dry powder is the sum of the mass of the positive electrode active material, the binder, the conductive agent and the compound A.
In the process of mixing ingredients, the compound A can neutralize residual alkali (such as LiOH, naOH and Na) remained on the surface of the positive electrode material 2 CO 3 ) The water absorption of the slurry is reduced, and the attack of the base pair binder is avoided, so that the viscosity of the slurry is stabilized, and the subsequent coating process is ensured to be smoothly carried out. If the added content is too low, the alkaline substances in the system cannot be completely neutralized, and if the added content is too high, sulfonic acid in the compound A erodes the positive electrode material, so that the positive electrode material is lost, the capacity is reduced, even metal ions are dissolved out, and potential safety hazards are brought. Therefore, the amount of compound a added is preferably 0.1 to 0.5% relative to the amount of the residual alkali on the surface of the positive electrode.
Meanwhile, the present invention is not particularly limited as to the slurry mixing preparation method, and methods known in the industry, including wet homogenization, semi-wet homogenization, etc., may be employed.
In addition, in another embodiment, a secondary battery is provided, which comprises a negative electrode sheet, a diaphragm, electrolyte and a battery shell, and further comprises the positive electrode sheet.
The secondary battery can be prepared by adopting the existing process (such as a lithium ion battery preparation process or a sodium ion battery preparation process), for example, the positive electrode plate, the diaphragm and the negative electrode plate are sequentially stacked to form a pole core or are manufactured into a pole core by a winding mode, the pole core is filled into a battery shell, electrolyte is filled into the battery shell, and then the battery shell is sequentially sealed, formed, separated and stood to prepare the secondary battery, and meanwhile, other components required by the secondary battery, such as the battery shell, the diaphragm, the electrolyte, the negative electrode and the like, are all commonly used devices in the field, and the invention is not limited to the above.
Further supplementary explanation is made below in connection with specific examples:
example 1:
1. preparation of positive plate
Firstly, ternary anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811), conductive carbon black, and polyvinylidene fluoride, taurine (r1=r2=r3=r4=h) are dispersed in N-methylpyrrolidone, and then wet, knead, and dispersion treatment is performed to obtain a positive electrode slurry;
wherein, NCM811: conductive carbon black: the weight ratio of polyvinylidene fluoride is 98:1:1, a step of; the mass of taurine is 0.1% of the total mass of the high nickel positive electrode material 811, the binder, the conductive agent, and taurine.
And coating the positive electrode active slurry on two surfaces of an aluminum foil, and then drying, rolling and cutting to obtain the required positive electrode plate.
2. Preparation of negative electrode
Dissolving a binder CMC (sodium carboxymethyl cellulose) in water, then adding a negative electrode material natural graphite, fully mixing and stirring, then adding SBR styrene butadiene rubber emulsion, and continuing mixing and stirring; then uniformly coating the negative electrode slurry on two sides of a copper foil with the thickness of 10 mu m, baking and drying at the temperature of 100 ℃, and rolling to obtain a negative electrode plate, wherein the negative electrode plate comprises the following materials in percentage by weight: graphite: CMC: sbr=96.5: 1.5:2.
3. preparation of lithium ion secondary battery
After the positive electrode, the negative electrode and the polyethylene diaphragm are respectively subjected to the working procedures of winding, assembling, sleeving into a battery shell, baking and the like, a proper amount of common electrolyte is injected into the battery aluminum shell, and the lithium ion secondary battery is manufactured after the working procedures of sealing, aging, formation, capacity division and the like, wherein the ratio of the mixed solvent in the electrolyte is specifically EC/EMC/dec=1: 1:1 (volume ratio), the concentration of LiPF6 is 1mol/L.
Comparative example 1:
in comparison with example 1, the materials were the same except that taurine was not added to the positive electrode sheet, and the preparation process was the same.
Example 2:
1. preparation of positive plate
Firstly, dispersing ternary anode material nickel iron manganese acid sodium (NFM 111), conductive carbon black, polyvinylidene fluoride and taurine (R1=R2=R3=R4=H) in N-methyl pyrrolidone, and then wetting, kneading and dispersing to obtain anode slurry;
wherein NFM111: conductive carbon black: the weight ratio of polyvinylidene fluoride is 97.5:1:1.5; the mass of taurine is 0.2% of the total mass of the positive electrode material NFM111, the binder, the conductive agent and the taurine;
and coating the positive electrode active slurry on two surfaces of an aluminum foil, and then drying, rolling and cutting to obtain the required positive electrode plate.
2. Preparation of negative electrode
Dissolving a binder CMC (sodium carboxymethyl cellulose) in water, then adding conductive carbon black and a negative electrode material hard carbon, fully mixing and stirring, then adding SBR styrene butadiene rubber emulsion, and continuing mixing and stirring; then uniformly coating the negative electrode slurry on two sides of a copper foil with the thickness of 10 mu m, baking and drying at the temperature of 100 ℃, and rolling to obtain a negative electrode plate, wherein the negative electrode plate comprises the following materials in percentage by weight: hard carbon: super-p CMC: sbr=94.5: 1.5:1.5:2.5.
3. Preparation of sodium ion secondary battery
The positive electrode, the negative electrode and the polyethylene diaphragm are respectively subjected to the working procedures of winding, assembling, sleeving into a battery shell, baking and the like, a proper amount of common electrolyte is injected into the battery aluminum shell for sealing, and the sodium ion secondary battery is prepared after the working procedures of aging, formation, capacity division and the like, wherein the ratio of the mixed solvent in the electrolyte is specifically EC/PC/dmc=0.45: 0.45:0.1 (volume ratio) the additive was 5wt.% vinylene carbonate FEC, wherein the concentration of NaPF6 was 0.8mol/L.
Comparative example 2:
compared with example 2, the preparation process was the same as that of the other materials except that taurine was not added to the positive electrode sheet.
Example 3:
1. preparation of positive plate
Firstly, ternary anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811), conductive carbon black, polyvinylidene fluoride, and methyl taurine (r1=r2=r3=h, r4=ch3) are dispersed in N-methylpyrrolidone, and then wet, knead, and dispersion treatment is performed to obtain a positive electrode slurry;
wherein, NCM811: conductive carbon black: the weight ratio of polyvinylidene fluoride is 98:1:1, the mass of the methyl taurine is 0.1% of the total mass of the high nickel positive electrode material 811, the binder, the conductive agent and the methyl taurine;
and coating the positive electrode active slurry on two surfaces of an aluminum foil, and then drying, rolling and cutting to obtain the required positive electrode plate.
2. Preparation of negative electrode
Dissolving a binder CMC (sodium carboxymethyl cellulose) in water, then adding a negative electrode material natural graphite, fully mixing and stirring, then adding SBR styrene butadiene rubber emulsion, and continuing mixing and stirring; then uniformly coating the negative electrode slurry on two sides of a copper foil with the thickness of 10 mu m, baking and drying at the temperature of 100 ℃, and rolling to obtain a negative electrode plate, wherein the negative electrode material comprises the following components in percentage by weight: graphite: CMC: sbr=96.5: 1.5:2.
3. preparation of lithium ion secondary battery
After the positive electrode, the negative electrode and the polyethylene diaphragm are respectively subjected to the working procedures of winding, assembling, sleeving into a battery shell, baking and the like, a proper amount of common electrolyte is injected into the battery aluminum shell for sealing, and the lithium ion secondary battery is prepared after the working procedures of aging, formation, capacity division and the like, wherein the ratio of the mixed solvent in the electrolyte is specifically EC/EMC/dec=1: 1:1 (volume ratio), the concentration of LiPF6 is 1mol/L.
Comparative example 3:
compared with example 3, the preparation process was the same as that of the other materials except that no methyltaurine was added to the positive electrode sheet.
Example 4:
1. preparation of positive plate
Firstly, dispersing ternary anode material nickel iron manganese acid sodium (NFM 111), conductive carbon black, polyvinylidene fluoride and taurine (R1=R2=R3=H; R4=CH3) in N-methyl pyrrolidone, and then wetting, kneading and dispersing to obtain anode slurry;
wherein NFM111: conductive carbon black: the weight ratio of polyvinylidene fluoride is 97.5:1:1.5, the mass of the methyl taurine is 0.2 percent of the total mass of the anode material NFM111, the binder, the conductive agent and the methyl taurine.
And coating the positive electrode active slurry on two surfaces of an aluminum foil, and then drying, rolling and cutting to obtain the required positive electrode plate.
2. Preparation of negative electrode
Dissolving a binder CMC (sodium carboxymethyl cellulose) in water, then adding conductive carbon black and a negative electrode material hard carbon, fully mixing and stirring, then adding SBR styrene butadiene rubber emulsion, and continuing mixing and stirring; then uniformly coating the negative electrode slurry on two sides of a copper foil with the thickness of 10 mu m, baking and drying at the temperature of 100 ℃, and rolling to obtain a negative electrode plate, wherein the negative electrode material comprises the following components in percentage by weight: hard carbon: super-p CMC: sbr=94.5: 1.5:1.5:2.5.
3. Preparation of sodium ion secondary battery
The positive electrode, the negative electrode and the polyethylene diaphragm are respectively subjected to the working procedures of winding, assembling, sleeving into a battery shell, baking and the like, a proper amount of common electrolyte is injected into the battery aluminum shell for sealing, and the sodium ion secondary battery is prepared after the working procedures of aging, formation, capacity division and the like, wherein the ratio of the mixed solvent in the electrolyte is specifically EC/PC/dmc=0.45: 0.45:0.1 (volume ratio) the additive was 5wt.% vinylene carbonate FEC, wherein the concentration of NaPF6 was 0.8mol/L.
Comparative example 4:
compared with example 4, the preparation process was the same as that of the other materials except that no methyltaurine was added to the positive electrode sheet.
The slurries and secondary batteries obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to stability test and charge-discharge cycle performance test, respectively, and the test results are shown in fig. 1 to 3.
The slurry stability testing method comprises the following steps: and taking the slurry with the same volume at room temperature, testing the viscosity value of the slurry at intervals, and drawing a change curve chart of the viscosity with time.
The cycle life test method comprises the following steps: charging to cut-off voltage with constant current and constant voltage of 0.5C at room temperature, cutting off current of 0.02C, standing for 30 min, discharging to cut-off voltage with 0.5C, standing for 30 min, repeating the charging and discharging steps, and stopping after reaching the test termination condition.
As can be seen from fig. 1, the viscosity change amount of the slurry is small after taurine or methyl taurine is added to the slurry, the stability and fluidity of the slurry are remarkably improved, while the viscosity of the slurry of the comparative example is rapidly increased with the increase of the shelf time, and the fluidity is deteriorated, which is a remarkable feature of the slurry being jelly-like; as apparent from the cycle graph of fig. 2, the lithium ion secondary battery made of the positive electrode sheet added with taurine or methyl taurine has a capacity remaining rate significantly higher than that of the comparative example after 600 weeks of cycle, and cycle performance significantly improved; as is also apparent from the cycle chart of fig. 3, the sodium ion secondary battery made of the positive electrode sheet added with taurine or methyltaurine has a significantly higher capacity remaining rate after 1600 weeks of cycle than the comparative example, and the cycle performance is also significantly improved.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The positive plate comprises a current collector and an active material layer attached to at least one surface of the current collector, and is characterized in that the active material layer comprises taurine compounds A, and the structural formula of the taurine compounds A is as follows:
wherein R1 and R2 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, alkylaminoalkyl and halogen; r3 and R4 are selected from any one or more of hydrogen, alkyl, cycloalkyl, aryl, alkenyl and aralkyl.
2. The positive electrode sheet according to claim 1, wherein R1 and R2 are selected from hydrogen; and R3 and R4 are selected from any one or more of hydrogen, alkyl and aralkyl.
3. The positive electrode sheet according to claim 1, wherein the active material layer further comprises at least a positive electrode active material, a conductive agent, and a binder.
4. The positive electrode sheet according to claim 3, wherein the positive electrode active material comprises a positive electrode material containing lithium or a positive electrode material containing sodium.
5. The positive electrode sheet according to claim 4, wherein the positive electrode active material includes any one or more of the following materials: lithium cobalt composite oxide and its modified matter, lithium manganese composite oxide and its modified matter, lithium nickel composite oxide and its modified matter, lithium iron phosphate composite oxide and its modified matter, lithium manganese phosphate composite oxide and its modified matter, lithium vanadium phosphate composite oxide and its modified matter, multi-element transition metal lithium oxide and its modified matter, and lithium-rich manganese multi-element transition metal lithium oxide and its modified matter.
6. The positive electrode sheet according to claim 4, wherein the positive electrode active material includes any one or more of the following materials: layered oxide positive electrode material, polyanion positive electrode material, prussian white positive electrode material, and Prussian blue positive electrode material.
7. The positive electrode sheet according to claim 1, wherein the content of the compound a is 0.02% to 1% of the total weight of the active material layer.
8. A method for producing a positive electrode sheet at least for producing the positive electrode sheet according to any one of claims 3 to 7, comprising the steps of:
mixing an anode active material, a conductive agent, a binder and a compound A, adding a solvent, and uniformly stirring to obtain electrode slurry; and (3) after the viscosity of the electrode slurry is regulated, coating the electrode slurry on a current collector, and drying to obtain the battery positive plate.
9. The method for preparing a positive electrode sheet according to claim 8, wherein the compound a is 0.02 to 1% of the total mass of the dry powder in the electrode slurry, and wherein the total mass of the dry powder is the sum of the mass of the positive electrode active material, the binder, the conductive agent and the compound a.
10. A secondary battery comprising a negative electrode sheet, a separator, an electrolyte, and a battery case, characterized by further comprising the positive electrode sheet according to any one of claims 3 to 7.
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