CN114824211A - Method for coating anode material precursor with tin base and anode material precursor - Google Patents
Method for coating anode material precursor with tin base and anode material precursor Download PDFInfo
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- CN114824211A CN114824211A CN202210433703.8A CN202210433703A CN114824211A CN 114824211 A CN114824211 A CN 114824211A CN 202210433703 A CN202210433703 A CN 202210433703A CN 114824211 A CN114824211 A CN 114824211A
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- 239000002243 precursor Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 239000010405 anode material Substances 0.000 title description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 10
- -1 sulfide ions Chemical class 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 239000010406 cathode material Substances 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000011247 coating layer Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 4
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a method for coating a precursor of a positive electrode material by tin, which comprises the following steps: (1) mixing nickel cobalt manganese hydroxide with a solution containing carbonate ions and sulfide ions; (2) adding a stannous source solution into the mixed solution obtained in the step (1) for reaction and carrying out solid-liquid separation to obtain a solid product; (3) and (3) soaking the solid product obtained in the step (2) in a over-vulcanized salt solution, carrying out solid-liquid separation, washing and drying to obtain the precursor of the positive electrode material. The cathode material prepared from the cathode material precursor prepared by the preparation method has excellent conductivity and lithium ion migration rate, and the cathode material is ensured to have better electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a method for coating a precursor of an anode material with tin and the precursor of the anode material.
Background
As a novel green power supply, the lithium ion battery has the advantages of high working voltage, long cycle life, light weight, less self-discharge, no memory effect, high cost performance and the like, and is widely applied to the fields of consumer electronics and new energy automobiles at present. The positive electrode material is one of the core parts of the lithium ion battery, determines the performance of the lithium ion battery, and limits the energy density, the power density and the cycle life of the lithium ion battery. It can be said that the development of the positive electrode material determines the development direction of the lithium ion battery.
With the rapid development in the fields of electric vehicles, intelligent electronic devices, and the like, there is an urgent need for high energy density lithium batteries having a long cycle life and high safety. The use of a positive electrode having a high voltage and a high specific capacity is an effective way to increase the energy density of the battery. The layered positive electrode material has a high theoretical specific capacity, so that the layered positive electrode material is widely concerned, but the application of the layered positive electrode material under high voltage has more problems and challenges, especially the problems of structural phase change at an interface with an electrolyte, transition metal dissolution, oxygen precipitation, continuous oxidative decomposition of the electrolyte and the like, and the application of the layered positive electrode material in a high-energy-density lithium battery is severely limited.
In order to solve the above problems, in the prior art, the structural performance and the electrochemical performance of particles can be optimized by forming a coating layer on the surface of a precursor of the positive electrode material, so that the corrosion resistance of the positive electrode material is improved, and the side reaction between the material and the electrolyte is reduced. The coating layer separates the material from the electrolyte while reducing the contact resistance between particles, so that the side reaction between the material and the electrolyte is reduced, and the corrosion of HF gas decomposed by the electrolyte to the cathode material is prevented.
However, most of the coating materials used in the existing method for preparing the precursor of the cathode material containing the coating layer are oxide materials with lower electronic conductivity, so that the resistivity of the cathode material is increased; and the coating layer on the prepared anode material precursor is too compact, so that the migration rate of lithium ions is hindered, and the electrochemical performance of the final anode material is reduced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for coating a precursor of a cathode material by tin and the precursor of the cathode material.
The technical purpose of the invention is realized by the following technical scheme:
a method for coating a precursor of a positive electrode material on a tin base comprises the following steps:
(1) mixing nickel cobalt manganese hydroxide with a solution containing carbonate ions and sulfide ions;
(2) adding a stannous source solution into the mixed solution obtained in the step (1) for reaction and carrying out solid-liquid separation to obtain a solid product;
(3) and (3) soaking the solid product obtained in the step (2) in a over-vulcanized salt solution, carrying out solid-liquid separation, washing and drying to obtain the precursor of the positive electrode material.
Preferably, in the step (1), the nickel-cobalt-manganese hydroxide is mixed with the solution containing carbonate ions and sulfide ions according to the solid-to-liquid ratio of 1g (1-5) mL.
Preferably, the concentration of carbonate ions in the solution containing carbonate ions and sulfide ions in step (1) is 0.1-1.0 mol/L.
Preferably, the concentration of the sulfate ions in the solution containing carbonate ions and sulfate ions in step (1) is 0.1 to 1.0 mol/L.
Preferably, the stannous source in the stannous source solution in step (2) is a soluble stannous salt.
Preferably, the stannous source in the stannous source solution in step (2) is at least one of stannous chloride and stannous sulfate.
Preferably, the concentration of stannous ion in the stannous source solution in the step (2) is 0.01-1 mol/L.
Preferably, the stannous source solution in the step (2) is added dropwise into the mixed solution in the step (1).
Preferably, the dripping speed of the stannous source solution in the step (2) is 25-50 mL/h.
Preferably, in the step (2), when the reaction is carried out until the pH of the mixed solution is 8 to 9, the reaction is stopped and solid-liquid separation is carried out.
Preferably, the salt of the oversulfide in the solution of the oversulfide in the step (3) is at least one of sodium oversulfide or ammonium oversulfide.
Preferably, the concentration of the persulfide in the solution of the persulfide in the step (3) is 0.1 to 1 mol/L.
Preferably, the solid product in the step (3) is mixed with the solution of the persulfate according to the solid-to-liquid ratio of 1g (1-5) mL.
Preferably, the soaking time in the step (3) is 1-24 h.
Preferably, the washing mode in the step (3) is washing with deionized water, and then washing with ethanol or acetone.
Preferably, the drying mode in the step (3) is vacuum drying at 50-80 ℃ for 2-12 h.
Preferably, the method for coating the positive electrode material precursor by the tin base comprises the following steps:
s1, preparing a stannous source solution with stannous ion concentration of 0.01-1mol/L, wherein the stannous source is at least one of stannous chloride and stannous sulfate;
s2, preparing a mixed solution of sodium carbonate and sodium sulfide, wherein the concentration of the sodium carbonate is 0.1-1.0mol/L, and the concentration of the sodium sulfide is 0.1-1.0 mol/L;
s3, adding the hydroxide of nickel, cobalt and manganese into the mixed solution prepared in the step (2) according to the solid-to-liquid ratio of 1g (1-5) mL;
s4, under the condition of continuously stirring at the stirring speed of 200-500r/min, dropwise adding the stannous source solution prepared in the step (1) into the mixed solution at the dropwise adding speed of 25-50 mL/h;
s5, stopping the reaction when the pH value of the mixed solution is detected to be 8-9, and carrying out solid-liquid separation to obtain a wet material;
s6, adding the wet material into 0.1-1mol/L sodium persulfate/ammonium persulfate solution according to the solid-to-liquid ratio of 1g (1-5) mL, and soaking for 1-24 h;
s7, after solid-liquid separation, washing the solid with deionized water, and then washing with ethanol or acetone;
and S8, after washing, drying for 2-12h in vacuum at 50-80 ℃ to obtain the precursor of the tin-based coated anode material.
The precursor of the cathode material is prepared by the preparation method.
The cathode material is formed by mixing and sintering a lithium source and the cathode material precursor.
A lithium ion battery comprising a positive electrode material as described above.
The invention has the beneficial effects that:
(1) the method comprises the steps of mixing nickel-cobalt-manganese hydroxide into a mixed solution containing carbonate ions and sulfide ions, dropwise adding a stannous source solution to generate a mixed precipitate of stannous hydroxide and stannous sulfide, coating the mixed precipitate on the surface of a precursor (nickel-cobalt-manganese hydroxide), finally further dissolving a coating layer on the surface of the precursor by using over-sulfurized salt, removing the stannous sulfide in the coating layer, and leaving the position originally occupied by the stannous sulfide in the coating layer of the precursor to be vacant, so that the coating layer becomes loose and porous, and further the precursor material with the porous coating layer is obtained.
The reaction equation is as follows: after the stannous source solution is dripped, stannous ions are hydrolyzed to generate stannous sulfide precipitate: sn (tin) 2+ +2OH - ＝Sn(OH) 2 ↓、Sn 2+ +S 2- SnS ↓coatinglayer in the over-sulfide salt solution, further dissolved: SnS + S 2 2- ＝SnS 3 2- 。
(2) The surface of the precursor prepared by the method is coated with a layer of stannous hydroxide, and when the precursor is sintered with a lithium source to prepare the anode material in the subsequent step, the coating layer can be dehydrated and oxidized to form stannic oxide with higher conductivity, so that the electronic conductivity of the anode material is improved; meanwhile, the positive electrode material inherits the morphological characteristics of the precursor, and the surface coating layer of the positive electrode material is of a porous structure, so that the mobility of lithium ions is further improved, the insertion and the extraction of lithium in the positive electrode material are facilitated, the side reaction of the positive electrode material body and the electrolyte is isolated, and the cycle performance of the material is improved.
Drawings
Fig. 1 is an SEM image of a positive electrode material precursor prepared in example 1 of the present invention, magnified 10000 times;
fig. 2 is an SEM image of the positive electrode material precursor prepared in example 1 of the present invention at a magnification of 100000 times.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a method for coating a precursor of a positive electrode material on a tin base comprises the following steps:
s1, preparing a stannous chloride solution with the concentration of 0.5 mol/L;
s2, preparing a mixed solution of sodium carbonate and sodium sulfide, wherein the concentration of the sodium carbonate is 0.5mol/L, and the concentration of the sodium sulfide is 0.5 mol/L;
s3, preparing nickel-cobalt-manganese hydroxide (molecular formula: Ni) 0.62 Mn 0.2 Co 0.18 (OH) 2 ) Adding the mixed solution prepared in the step (2) according to the solid-liquid ratio of 1g:3 mL;
s4, under the condition of continuous stirring at the stirring speed of 300r/min, dropwise adding the stannous chloride solution prepared in the step (1) into the mixed solution at the dropping speed of 35 mL/h;
s5, stopping the reaction when the pH value of the mixed solution is detected to be 8-9, and carrying out solid-liquid separation to obtain a wet material;
s6, adding the wet material into 0.5mol/L sodium persulfate/ammonium persulfate solution according to the solid-liquid ratio of 1g:3mL, and soaking for 12 h;
s7, after solid-liquid separation, washing the solid with deionized water, and then washing with ethanol;
and S8, after washing, carrying out vacuum drying for 7h at 65 ℃ to obtain the precursor of the tin-based coated anode material.
A positive electrode material precursor prepared by the preparation method as described above, wherein an SEM image at 10000 times is shown in fig. 1, and an SEM image at 100000 times is shown in fig. 2.
Example 2:
a method for coating a precursor of a positive electrode material on a tin base comprises the following steps:
s1, preparing a stannous chloride solution with the concentration of 0.01 mol/L;
s2, preparing a mixed solution of sodium carbonate and sodium sulfide, wherein the concentration of the sodium carbonate is 0.1mol/L, and the concentration of the sodium sulfide is 0.1 mol/L;
s3, preparing hydroxide of nickel, cobalt and manganese (molecular formula: Ni) 0.62 Mn 0.2 Co 0.18 (OH) 2 ) Adding the mixed solution prepared in the step (2) according to the solid-liquid ratio of 1g:1 mL;
s4, under the condition of continuous stirring at the stirring speed of 200r/min, dropwise adding the stannous chloride solution prepared in the step (1) into the mixed solution at the dropwise adding speed of 25 mL/h;
s5, stopping the reaction when the pH value of the mixed solution is detected to be 8-9, and carrying out solid-liquid separation to obtain a wet material;
s6, adding the wet material into 0.1mol/L sodium persulfate/ammonium persulfate solution according to the solid-liquid ratio of 1g:1mL, and soaking for 1 h;
s7, after solid-liquid separation, washing the solid with deionized water, and then washing with ethanol;
and S8, after washing, carrying out vacuum drying for 12h at 50 ℃ to obtain the precursor of the tin-based coated anode material.
The precursor of the cathode material is prepared by the preparation method.
Example 3:
a method for coating a precursor of a positive electrode material on a tin base comprises the following steps:
s1, preparing a stannous sulfate solution with the concentration of 1 mol/L;
s2, preparing a mixed solution of sodium carbonate and sodium sulfide, wherein the concentration of the sodium carbonate is 1.0mol/L, and the concentration of the sodium sulfide is 1.0 mol/L;
s3, preparing hydroxide of nickel, cobalt and manganese (molecular formula: Ni) 0.85 Mn 0.08 Co 0.7 (OH) 2 ) Adding the mixed solution prepared in the step (2) according to the solid-liquid ratio of 1g:5 mL;
s4, under the condition of continuous stirring at the stirring speed of 500r/min, dropwise adding the stannous sulfate solution prepared in the step (1) into the mixed solution at the dropwise adding speed of 50 mL/h;
s5, stopping the reaction when the pH value of the mixed solution is detected to be 8-9, and carrying out solid-liquid separation to obtain a wet material;
s6, adding the wet material into 1mol/L sodium persulfate/ammonium persulfate solution according to the solid-liquid ratio of 1g:5mL, and soaking for 24 h;
s7, after solid-liquid separation, washing the solid with deionized water, and then washing with acetone;
and S8, after washing, drying for 2h in vacuum at 80 ℃ to obtain the precursor of the tin-based coated anode material.
The precursor of the cathode material is prepared by the preparation method.
Test example:
taking the nickel-cobalt-manganese hydroxide adopted in the examples 1-3 as a comparative example 1-3, mixing the positive electrode material precursor obtained in the examples 1-3 and the nickel-cobalt-manganese hydroxide adopted in the examples 1-3 as raw materials with lithium hydroxide according to the Li/(Ni + Co + Mn) molar ratio of 1.04, heating to 750 ℃ in an oxygen atmosphere furnace, preserving the temperature for 10 hours, and then cooling, crushing and sieving along with the furnace to obtain the corresponding positive electrode material. The conductivity performance of each positive electrode material was tested, and the results are shown in table 1:
table 1: conductive performance test results of the positive electrode material
| Conductivity (s/cm) | Volume resistivity (omega cm) | |
| Example 1 | 3.46*10 -2 | 36.1 |
| Example 2 | 1.73*10 -2 | 38.9 |
| Example 3 | 3.98*10 -2 | 34.3 |
| Comparative example 1 | 2.88*10 -3 | 358.6 |
| Comparative example 2 | 2.84*10 -3 | 359.3 |
| Comparative example 3 | 2.86*10 -3 | 358.8 |
As can be seen from table 1, the positive electrode material prepared from the precursor of the positive electrode material of the present invention has excellent conductivity, and the conductivity thereof is less than 3.98 × 10 -2 s/cm and volume resistivity of less than 34.3 omega cm, and meanwhile, comparing example 1 with comparative example 1, example 2 with comparative example 2, and example 3 with comparative example 3, respectively, it can be seen that the conductivity of the cathode material prepared by the tin-based coated cathode material precursor of the present invention is far better than that of the cathode material prepared by the cathode material precursor without tin-based coating.
Meanwhile, taking each positive electrode material, acetylene black as a conductive agent and PVDF as a binder, weighing the active material, the conductive agent and the binder according to a ratio of 92:4:4, adding a certain amount of organic solvent NMP, stirring, coating on an aluminum foil to prepare a positive electrode plate, taking a metal lithium plate as a negative electrode, and preparing the lithium ion battery in a glove box filled with argon. At normal temperature, the material is charged and discharged at the current of 3.6A, and the first effect (%), the 0.1C specific discharge capacity, the 1C specific discharge capacity and the 300-cycle retention rate (%) are tested. The test results are shown in table 2:
table 2: results of cell electrochemical performance testing
As can be seen from table 2, after the positive electrode material prepared from the positive electrode material precursor of the present invention is assembled into a battery, the battery has excellent electrochemical performance, the first efficiency of the battery can reach 92.3% or more, the 0.1C specific discharge capacity can reach 192.1mAh/g or more, the 1C specific discharge capacity can reach 178.4mAh/g or more, and the capacity retention rate can reach 90.1% or more after 0.1C cycle 300 times, and meanwhile, by comparing example 1 with comparative example 1, example 2 with comparative example 2, and example 3 with comparative example 3, it can be seen that after the positive electrode material prepared from the tin-based coated positive electrode material precursor of the present invention is assembled into a battery, the electrochemical performance of the battery is superior to that of the battery assembled from the positive electrode material prepared from the positive electrode material precursor which is not coated with tin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for coating a precursor of a positive electrode material by a tin base is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing nickel cobalt manganese hydroxide with a solution containing carbonate ions and sulfide ions;
(2) adding a stannous source solution into the mixed solution obtained in the step (1) for reaction and carrying out solid-liquid separation to obtain a solid product;
(3) and (3) soaking the solid product obtained in the step (2) in a over-vulcanized salt solution, carrying out solid-liquid separation, washing and drying to obtain the precursor of the positive electrode material.
2. The method of claim 1, wherein the precursor comprises: in the step (1), the nickel-cobalt-manganese hydroxide is mixed with a solution containing carbonate ions and sulfide ions according to the solid-to-liquid ratio of 1g (1-5).
3. The method of claim 1, wherein the precursor comprises: the concentration of the sulfur ions in the solution containing the carbonate ions and the sulfur ions in the step (1) is 0.1-1.0 mol/L.
4. The method of claim 1, wherein the precursor of the tin-based clad positive electrode material comprises: in the step (2), the concentration of stannous ions in the stannous source solution is 0.01-1 mol/L.
5. The method of claim 1, wherein the precursor comprises: and (3) adding the stannous source solution in the step (2) dropwise into the mixed solution in the step (1).
6. The method of claim 1, wherein the precursor comprises: and (3) stopping the reaction in the step (2) until the pH value of the mixed solution is 8-9, and carrying out solid-liquid separation.
7. The method of claim 1, wherein the precursor comprises: the concentration of the over-vulcanized salt in the over-vulcanized salt solution in the step (3) is 0.1-1 mol/L.
8. The method of claim 1, wherein the precursor comprises: and (3) mixing the solid product in the step (3) with a solution of a persulfate according to the solid-to-liquid ratio of 1g (1-5) mL.
9. A positive electrode material precursor characterized by: prepared by the preparation method of any one of claims 1 to 8.
10. A positive electrode material characterized in that: the positive electrode material precursor according to claim 9 is mixed with a lithium source and sintered.
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| CN202210433703.8A CN114824211B (en) | 2022-04-24 | 2022-04-24 | Method for coating positive electrode material precursor by tin base and positive electrode material precursor |
| DE112023000117.0T DE112023000117T5 (en) | 2022-04-24 | 2023-02-08 | Method for producing a cathode material precursor by tin-based coating, and cathode material precursor |
| PCT/CN2023/074953 WO2023207249A1 (en) | 2022-04-24 | 2023-02-08 | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
| GB2314779.6A GB2625624A (en) | 2022-04-24 | 2023-02-08 | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
| HU2400048A HUP2400048A1 (en) | 2022-04-24 | 2023-02-08 | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
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| KR20180105762A (en) * | 2017-03-15 | 2018-10-01 | 전자부품연구원 | Ni-rich positive composition for lithium secondary battery using spherical transition metal complex hydroxide with nano-titanate and manufacturing method thereof |
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| CN113929152A (en) * | 2020-07-14 | 2022-01-14 | 恒大新能源技术(深圳)有限公司 | Composite material precursor, composite material, preparation method of composite material and positive plate |
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