CN112340786A - Modification method of positive electrode material, modified positive electrode material and lithium ion battery - Google Patents
Modification method of positive electrode material, modified positive electrode material and lithium ion battery Download PDFInfo
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- CN112340786A CN112340786A CN202011231672.5A CN202011231672A CN112340786A CN 112340786 A CN112340786 A CN 112340786A CN 202011231672 A CN202011231672 A CN 202011231672A CN 112340786 A CN112340786 A CN 112340786A
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- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 67
- 238000002715 modification method Methods 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 61
- 239000002270 dispersing agent Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 31
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- 239000010405 anode material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 18
- 230000000051 modifying effect Effects 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 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 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 235000011083 sodium citrates Nutrition 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229910013191 LiMO2 Inorganic materials 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl glucoside Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229930182478 glucoside Natural products 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 150000003482 tantalum compounds Chemical class 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a modification method of a positive electrode material, the modified positive electrode material and a lithium ion battery. The method comprises the following steps: mixing the positive electrode material with a dispersant and a modified additive in a liquid phase, heating, carrying out solid-liquid separation to obtain a solid, and calcining to obtain the modified positive electrode material. According to the modification method provided by the invention, the contact uniformity of the modification additive and the anode material can be improved by using the dispersing agent, the doping or coating of the obtained modified product is more uniform, the electrochemical performance of the material is more favorably improved, the mixing and discharging degree of lithium elements and other metal elements in the anode material can be reduced, a lithium ion diffusion channel can be improved, the residual lithium and pH value on the surface are reduced, good chemical stability is realized, a good ion transmission channel is ensured, and the rate capability is improved while good cycle performance is maintained.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a modification method of a positive electrode material, the modified positive electrode material and a lithium ion battery.
Background
In order to meet the market demand, lithium ion batteries are developing towards high voltage (> 4.35V), but electrochemical properties such as cycle performance, storage performance, rate performance and the like of the cathode material are deteriorated under high operating voltage. To solve these problems of the cathode material, the industry and academia tend to improve the structural stability and thermal stability of the ternary material by doping and cladding. However, the conventional modification method usually needs to dope the material at a higher temperature, the higher temperature can cause the surface impurity lithium to be rapidly increased and also easily damage the structure of the material, and the cycle performance of the material is easily reduced, and in the prior art, the material coated with TiO is obtained by secondary sintering or more sintering2、Li3PO4、ZrO2、V2O5、Al2O3、MoO3And the electrochemical performance of the ternary material is improved by the anode material of the materials.
CN107819114A is obtained by premixing a single-crystal nickel-cobalt-manganese composite precursor and a tantalum compound at a high speed, and then mixing a mixture of the single-crystal nickel-cobalt-manganese composite precursor and the tantalum compound with a common polycrystalline nickel-cobalt-manganese composite precursor at a high speed.
CN107799739A is obtained by premixing a single-crystal nickel-cobalt-manganese composite precursor and a vanadium compound at an ultra-high speed, and then mixing a mixture of the single-crystal nickel-cobalt-manganese composite precursor and the vanadium compound with a common polycrystalline nickel-cobalt-manganese composite precursor at a high speed.
However, the method cannot solve the problem of material interface instability, has limited performance of improving the material, and is not beneficial to production and use because of high toxicity of metal vanadium.
CN108400309A is sintered after lithium salt and hydroxide precursor are added into a ball mill to be mixed, then the single crystal material, the coating matrix and deionized water are added into a stirring tank, soluble phosphate and soluble aluminum salt are added into the stirring tank, after post-treatment, the initially coated high-voltage single crystal ternary positive electrode material is subjected to heat treatment for 4-10h at the temperature of 500-850 ℃, and the composite coated high-voltage single crystal ternary positive electrode material is obtained. None of these methods can ensure the uniformity of the coating layer, and are not suitable for large-scale production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modification method of a positive electrode material, the modified positive electrode material and a lithium ion battery. The modification method provided by the invention has the advantages that the dispersant is introduced to assist the modification of the anode material, the process is simple, the coating doping amount is uniform, the production cost is low, and the method is suitable for the preparation of various anode materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for modifying a positive electrode material, the method comprising the steps of:
mixing the positive electrode material with a dispersant and a modified additive in a liquid phase, heating, carrying out solid-liquid separation to obtain a solid, and calcining to obtain the modified positive electrode material.
According to the modification method provided by the invention, the anode material is mixed with the dispersing agent and the modification additive, the dispersing agent is introduced to help coating or the dopant is more uniformly mixed with the active substance, and the modified anode material is obtained by calcining, so that the electrochemical performance of the material is improved; the method can reduce the mixed discharging degree of lithium element and other metal elements in the anode material, improve the lithium ion diffusion channel, reduce the residual lithium and pH value on the surface, ensure a good ion transmission channel while having good chemical stability, and improve the multiplying power performance while maintaining good cycle performance.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the dispersant includes any one or a combination of at least two of sodium dodecylbenzene sulfonate, alkyl glucoside, fatty glyceride, sodium hexametaphosphate, sodium tripolyphosphate, carboxymethyl cellulose, sodium citrate, ammonium salt, polycarboxylic acid, polyacrylic acid (PAA), and sodium polyacrylate (MA-a). The dispersing agents are adopted because the dispersing agents can obviously improve the contact interface of the anode material and the modifying agent in a liquid phase, enhance the stability of the suspension, ensure that the modifying agent can be uniformly and tightly distributed on the surface of the anode material, and realize uniform coating modification on the surface of the anode material.
Preferably, the ammonium salt comprises ammonium polyacrylate.
Preferably, the polycarboxylic acid comprises polyethylene glycol acrylate.
Preferably, the modifying additive is a metal salt.
Preferably, the metal element in the metal salt includes any one or a combination of at least two of sodium, zinc, aluminum, cobalt, zirconium, nickel, or titanium.
Preferably, the metal salt is a soluble metal salt.
As a preferable technical solution of the present invention, the positive electrode material includes any one or a combination of at least two of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, and a lithium-rich manganese-based positive electrode material. The method provided by the invention can be applied to modification of various types of cathode materials, and is not limited to individual types of cathode materials.
Preferably, the chemical formula of the nickel cobalt lithium manganate is Li1+nNixCoyMn(1-x-y-n)O2Where 0. ltoreq. n < 1, e.g. n is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 etc., 0 < x < 1, e.g. x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 etc., 0 < y < 1, e.g. y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 etc.
Preferably, the chemical formula of the lithium-rich manganese-based cathode material is xLi2MnO3·(1-x)LiMO2Wherein 0 < x < 1, for example x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc., and M is any one or a combination of at least two of Ni, Co or Mn.
Preferably, the lithium nickel cobalt aluminate has the formula LiNi0.8Co0.15Al0.05O2。
Preferably, the temperature of the heat treatment is 40-80 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
Preferably, the time of the heat treatment is 1 to 5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, etc.
Preferably, the heating treatment is accompanied by stirring.
In a preferred embodiment of the present invention, the mass of the dispersant is 0.1 to 5 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt% of the mass of the positive electrode material. In the invention, if the dispersant is too much, the dispersant is agglomerated, the suspension is settled, and the difficulty of subsequent washing and filtering is increased; if the amount of the dispersant is too small, the positive electrode material and the modifier may not be completely dispersed, resulting in uneven mixing.
Preferably, the mass of the modifying additive is 0.1 to 1 wt% of the mass of the positive electrode material, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%, and the like. In the invention, if the modifying additive is too much, the surface coating layer of the anode material is too thick, and the electrochemical performance of the anode material is influenced; if the modifying additive is too little, the coating layer of the positive electrode material is incomplete, and the modifying effect of the positive electrode material is affected.
Preferably, the method for mixing the cathode material with the dispersant and the modifying additive in the liquid phase is as follows: mixing a dispersing agent and a solvent, adding a modified additive after stirring and dispersing, stirring and mixing, and adding a positive electrode material;
preferably, the stirring time for adding the modifying additive and stirring and mixing is 10-60min, such as 10min, 20min, 30min, 40min, 50min or 60 min.
In a preferred embodiment of the present invention, the solid-liquid separation method is filtration separation.
Preferably, the temperature of the calcination is 400-700 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, etc. In the invention, if the temperature for calcining the solid obtained by solid-liquid separation is too high, the particles of the anode material grow up, the material performance is influenced, and the cost is increased; if the calcining temperature is too low, the modifier can not completely react, the integrity of the coating is poor, and the modification effect on the cathode material is influenced.
Preferably, the calcination is carried out for a time of 2 to 8h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc.
Preferably, after the solid-liquid separation and before the calcination, the method further comprises: and washing and drying the solid obtained by solid-liquid separation.
As a preferred technical scheme of the invention, the cathode material is prepared by the following method: and mixing the lithium salt with the hydroxide precursor, and calcining the obtained mixed product to obtain the cathode material.
In the method for preparing the cathode material, the mixing is ball milling mixing.
Preferably, in the method for preparing the cathode material, the mixing time is 2-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h.
Preferably, in the method for preparing the cathode material, the atmosphere for calcination is air and/or oxygen. The oxygen can be ordinary oxygen (99.6-99.9%) or high-purity oxygen (99.99%).
Preferably, in the method of preparing the positive electrode material, the calcination is a secondary calcination.
Preferably, in the two-stage calcination, the temperature of the first-stage calcination is 350-550 ℃, such as 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 550 ℃, and the time of the first-stage calcination is 1-5h, such as 1h, 2h, 3h, 4h or 5 h.
Preferably, in the second stage calcination, the temperature of the second stage calcination is 600-.
In the invention, the purpose of the two-stage calcination is to ensure that the raw materials are reacted to generate the cathode material with high crystallinity and no impurity phase.
As a further preferable embodiment of the modification method of the present invention, the method comprises the steps of:
(1) ball-milling and mixing the lithium salt and the hydroxide precursor for 2-10h, and performing secondary calcination on the obtained mixed product in air and/or oxygen, wherein the temperature of the first-stage calcination is 350-550 ℃, the time of the first-stage calcination is 1-5h, the temperature of the second-stage calcination is 600-1000 ℃, and the time of the second-stage calcination is 2-12h, so as to obtain the anode material;
(2) mixing a dispersing agent and a solvent, adding a modified additive after stirring and dispersing, stirring and mixing for 10-60min, adding the anode material obtained in the step (1), carrying out heat treatment for 1-5h at 40-80 ℃ under the stirring condition, filtering to obtain a solid, washing and drying the solid, and calcining for 2-8h at 400-700 ℃ to obtain a modified anode material;
the dispersing agent comprises any one or the combination of at least two of sodium hexametaphosphate, sodium tripolyphosphate, carboxymethyl cellulose, sodium citrate, ammonium salt, polycarboxylic acid substances, polyacrylic acid and sodium polyacrylate; the modified additive is metal salt, the metal element in the metal salt comprises any one or the combination of at least two of sodium, zinc, aluminum, cobalt, zirconium, nickel or titanium, the mass of the dispersing agent is 0.1-5 wt% of the mass of the anode material, and the mass of the modified additive is 0.1-1 wt% of the mass of the anode material.
In a second aspect, the present invention provides a modified cathode material obtained by the modification method of the first aspect.
In a third aspect, the invention provides a lithium ion battery comprising the modified cathode material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the modification method provided by the invention, the contact uniformity of the modification additive and the anode material can be improved by using the dispersing agent, the doping or coating of the obtained modified product is more uniform, the electrochemical performance of the material is more favorably improved, the mixing and discharging degree of lithium elements and other metal elements in the anode material can be reduced, a lithium ion diffusion channel can be improved, the residual lithium and pH value on the surface are reduced, good chemical stability is realized, a good ion transmission channel is ensured, and the rate capability is improved while good cycle performance is maintained. The first cycle charging specific capacity of the modified anode material provided by the invention can reach 250mAh/g, the first cycle efficiency can reach 95%, and the 100 cycle capacity retention rate can reach 96%.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example modified the positive electrode material as follows:
mixing a dispersant (sodium dodecyl benzene sulfonate) with a solvent (water), stirring and dispersing, adding a modified additive (aluminum nitrate), stirring and mixing for 35min, and adding the positive electrode material (nickel cobalt lithium manganate LiNi)0.8Co0.1Mn0.1O2) And carrying out heat treatment at 60 ℃ for 3h under the stirring condition, filtering to obtain a solid, washing and drying the solid, and calcining at 550 ℃ for 5h to obtain the modified cathode material.
Wherein the mass of the dispersing agent is 3 wt% of the mass of the positive electrode material, and the mass of the modifying additive is 0.5 wt% of the mass of the positive electrode material.
The positive electrode material (LiNi-Co-Mn acid lithium LiNi)0.8Co0.1Mn0.1O2) The preparation method comprises the following steps:
lithium salt (lithium hydroxide) and hydroxide precursor (Ni)0.8Co0.1Mn0.1(H O)2) Ball-milling and mixing for 6h according to the molar ratio of 1.05:1, and performing two-stage calcination on the obtained mixed product in oxygen, wherein the temperature of the first-stage calcination is 450 ℃, and the time of the first-stage calcinationThe temperature of the second stage calcination is 800 ℃, the time of the second stage calcination is 7h, and the anode material is obtained.
Example 2
This example modified the positive electrode material as follows:
mixing a dispersant (sodium tripolyphosphate) and a solvent (water), stirring and dispersing, adding a modified additive (zirconium nitrate), stirring and mixing for 10min, and adding the positive electrode material (lithium cobaltate LiCoO)2) And carrying out heat treatment for 5h at 40 ℃ under the stirring condition, filtering to obtain a solid, washing and drying the solid, and calcining for 8h at 400 ℃ to obtain the modified cathode material.
Wherein the mass of the dispersing agent is 0.1 wt% of the mass of the positive electrode material, and the mass of the modifying additive is 1 wt% of the mass of the positive electrode material.
The positive electrode material (lithium cobaltate LiCoO)2) The preparation method comprises the following steps:
and (2) ball-milling and mixing lithium carbonate and cobalt carbonate (in a molar ratio of 1:2) for 2 hours, and performing secondary calcination on the obtained mixed product in air, wherein the temperature of the first-stage calcination is 350 ℃, the time of the first-stage calcination is 5 hours, the temperature of the second-stage calcination is 600 ℃, and the time of the second-stage calcination is 12 hours, so as to obtain the cathode material.
Example 3
This example modified the positive electrode material as follows:
mixing a dispersant (sodium polyacrylate) with a solvent (water), stirring and dispersing, adding a modified additive (titanium chloride), stirring and mixing for 60min, and adding the positive electrode material (lithium-rich manganese-based positive electrode material 0.5 Li)2MnO3·0.5LiMO2And M is Co), performing heat treatment at 80 ℃ for 1h under the stirring condition, filtering to obtain a solid, washing and drying the solid, and calcining at 700 ℃ for 2h to obtain the modified cathode material.
Wherein the mass of the dispersing agent is 5 wt% of the mass of the positive electrode material, and the mass of the modifying additive is 0.1 wt% of the mass of the positive electrode material.
The positive electrode material (lithium-rich manganese-based positive electrode material 0.5 Li)2MnO3·0.5LiMO2M is Co) was prepared as follows:
and ball-milling and mixing the lithium carbonate and other metal salts according to the stoichiometric ratio for 2h, and performing secondary calcination on the obtained mixed product in air, wherein the temperature of the first-stage calcination is 550 ℃, the time of the first-stage calcination is 1h, the temperature of the second-stage calcination is 1000 ℃, and the time of the second-stage calcination is 2h, so as to obtain the cathode material.
Example 4
In this example, the modification method was the same as that provided in example 1 except that the dispersant was changed to the polycarboxylic acid polyethylene glycol acrylate, and the positive electrode material used for the modification was also completely the same as that of example 1.
Example 5
This example was identical to example 1 in all the modification methods except that the dispersant was changed to ammonium polyacrylate, and the positive electrode material used for the modification was also identical to example 1.
Example 6
This example was identical to the modification method provided in example 1 except that the mass of the dispersant was 0.05 wt% of the mass of the positive electrode material, and the positive electrode material used for the modification was also identical to that of example 1.
Example 7
This example was identical to the modification method provided in example 1 except that the mass of the dispersant was 7 wt% of the mass of the positive electrode material, and the positive electrode material used for the modification was also identical to example 1.
Comparative example 1
This comparative example was identical to the modification method provided in example 1 except that no dispersant was used, and the positive electrode material used for the modification was also identical to example 1.
Test method
Taking the modified cathode materials provided by the examples and the comparative examples as cathode active substances, acetylene black as a conductive agent and PVDF as a binder, wherein the mass percentages are as follows: 10: 10 in proportion is dissolved in NMP and mixed, the solid content is controlled to be 50 percent, the mixture is coated on an aluminum foil current collector and is dried in vacuum to prepare the anodePole pieces; then 1mol/L LiPF6The CR2032 button cell was assembled with EC + DMC + EMC (v/v 1:1) electrolyte, Celgard2400 separator, lithium metal sheet, housing using conventional manufacturing process and tested with the LAND cell test system.
The obtained battery is subjected to charge and discharge tests at 25 +/-2 ℃, the charge and discharge multiplying power is 0.2C, and the first cycle charging specific capacity, the first cycle efficiency and the 100 cycle performance are respectively tested. Wherein the charge and discharge voltage of NCM811 in example 1 is 2.8-4.25V, the test voltage range of lithium cobaltate in example 2 is 2.8-4.4V, and the test voltage range of lithium manganese rich material in example 3 is 2.8-4.5V. The test results are shown in table 1:
TABLE 1
It can be known from the above examples and comparative examples that in examples 1 to 5, the use of the dispersant can improve the contact uniformity between the modified additive and the positive electrode material, and the doping or coating of the obtained modified product is more uniform, which is more beneficial to improving the electrochemical performance of the material, so that not only can the mixing and discharging degree of lithium element and other metal elements in the positive electrode material be reduced, but also the channel for lithium ion diffusion can be improved, the residual lithium and pH on the surface can be reduced, good chemical stability can be achieved, good ion transmission channel can be ensured, and the rate performance can be improved while maintaining good cycle performance.
Example 6 too little dispersant failed to achieve uniform and stable dispersion of the positive electrode material and modifier in the liquid phase, resulting in insufficient mixing of the positive electrode material and modifier with each other and uneven distribution of the components in the final product.
Example 7, too much dispersant can cause the agglomeration of the dispersant, the sedimentation of the suspension, and too much residual dispersant in the finished product, which affects the electrochemical performance of the cathode material.
Comparative example 1 does not use a dispersant, a stable contact between the positive electrode material and the modifier cannot be formed, mixing is not uniform, uniform coating and doping modification of the positive electrode material cannot be achieved, inconsistency of components deteriorates electrochemical properties of the positive electrode material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for modifying a positive electrode material, the method comprising the steps of:
mixing the positive electrode material with a dispersant and a modified additive in a liquid phase, heating, carrying out solid-liquid separation to obtain a solid, and calcining to obtain the modified positive electrode material.
2. The modification method according to claim 1, wherein the dispersant comprises any one or a combination of at least two of sodium dodecylbenzene sulfonate, alkyl glucoside, fatty glyceride, sodium hexametaphosphate, sodium tripolyphosphate, carboxymethyl cellulose, sodium citrate, ammonium salt, polycarboxylic acid, polyacrylic acid, and sodium polyacrylate;
preferably, the ammonium salt comprises ammonium polyacrylate;
preferably, the polycarboxylic acid comprises polyethylene glycol acrylate;
preferably, the modifying additive is a metal salt;
preferably, the metal element in the metal salt comprises any one or a combination of at least two of sodium, zinc, aluminum, cobalt, zirconium, nickel or titanium;
preferably, the metal salt is a soluble metal salt.
3. The modification method according to claim 1 or 2, wherein the positive electrode material comprises any one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide or a lithium rich manganese based positive electrode material or a combination of at least two thereof;
preferably, the chemical formula of the nickel cobalt lithium manganate is Li1+nNixCoyMn(1-x-y-n)O2Wherein n is more than or equal to 0 and less than 1, x is more than 0 and less than 1, and y is more than 0 and less than 1;
preferably, the chemical formula of the lithium-rich manganese-based cathode material is xLi2MnO3·(1-x)LiMO2Wherein x is more than 0 and less than 1, and M is any one or the combination of at least two of Ni, Co or Mn;
preferably, the temperature of the heating treatment is 40-80 ℃;
preferably, the time of the heat treatment is 1-5 h;
preferably, the heating treatment is accompanied by stirring.
4. The modification method according to any one of claims 1 to 3, wherein the mass of the dispersant is 0.1 to 5 wt% of the mass of the positive electrode material;
preferably, the mass of the modified additive is 0.1-1 wt% of the mass of the cathode material;
preferably, the method for mixing the cathode material with the dispersant and the modifying additive in the liquid phase is as follows: mixing a dispersing agent and a solvent, adding a modified additive after stirring and dispersing, stirring and mixing, and adding a positive electrode material;
preferably, the stirring time for adding the modifying additive and stirring and mixing is 10-60 min.
5. The modification method according to any one of claims 1 to 4, wherein the solid-liquid separation method is a filtration separation;
preferably, the temperature of the calcination is 400-700 ℃;
preferably, the calcination time is 2-8 h;
preferably, after the solid-liquid separation and before the calcination, the method further comprises: and washing and drying the solid obtained by solid-liquid separation.
6. The modification method according to any one of claims 1 to 5, wherein the positive electrode material is prepared by: and mixing the lithium salt with the hydroxide precursor, and calcining the obtained mixed product to obtain the cathode material.
7. The modification method according to claim 6, wherein in the method for producing a positive electrode material, the mixing is ball-milling mixing;
preferably, in the method for preparing the cathode material, the mixing time is 2-10 h;
preferably, in the method for preparing the cathode material, the atmosphere for calcining is air and/or oxygen;
preferably, in the method for preparing the cathode material, the calcination is a two-stage calcination;
preferably, in the two-stage calcination, the temperature of the first-stage calcination is 350-550 ℃, and the time of the first-stage calcination is 1-5 h;
preferably, in the second-stage calcination, the temperature of the second-stage calcination is 600-1000 ℃, and the time of the second-stage calcination is 2-12 h.
8. Modification process according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1) ball-milling and mixing the lithium salt and the hydroxide precursor for 2-10h, and performing secondary calcination on the obtained mixed product in air and/or oxygen, wherein the temperature of the first-stage calcination is 350-550 ℃, the time of the first-stage calcination is 1-5h, the temperature of the second-stage calcination is 600-1000 ℃, and the time of the second-stage calcination is 2-12h, so as to obtain the anode material;
(2) mixing a dispersing agent and a solvent, adding a modified additive after stirring and dispersing, stirring and mixing for 10-60min, adding the anode material obtained in the step (1), carrying out heat treatment for 1-5h at 40-80 ℃ under the stirring condition, filtering to obtain a solid, washing and drying the solid, and calcining for 2-8h at 400-700 ℃ to obtain a modified anode material;
the dispersing agent comprises any one or the combination of at least two of sodium hexametaphosphate, sodium tripolyphosphate, carboxymethyl cellulose, sodium citrate, ammonium salt, polycarboxylic acid substances, polyacrylic acid and sodium polyacrylate; the modified additive is metal salt, the metal element in the metal salt comprises any one or the combination of at least two of sodium, zinc, aluminum, cobalt, zirconium, nickel or titanium, the mass of the dispersing agent is 0.1-5 wt% of the mass of the anode material, and the mass of the modified additive is 0.1-1 wt% of the mass of the anode material.
9. A modified positive electrode material obtained by the modification method according to any one of claims 1 to 8.
10. A lithium ion battery comprising the modified cathode material of claim 9.
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Application publication date: 20210209 |