CN113437270A - Double-layer coating modified lithium ion battery anode material powder and preparation method thereof - Google Patents
Double-layer coating modified lithium ion battery anode material powder and preparation method thereof Download PDFInfo
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- CN113437270A CN113437270A CN202110666675.XA CN202110666675A CN113437270A CN 113437270 A CN113437270 A CN 113437270A CN 202110666675 A CN202110666675 A CN 202110666675A CN 113437270 A CN113437270 A CN 113437270A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 105
- 238000000576 coating method Methods 0.000 title claims abstract description 105
- 239000010405 anode material Substances 0.000 title claims abstract description 68
- 239000000843 powder Substances 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000011247 coating layer Substances 0.000 claims abstract description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 239000002077 nanosphere Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 31
- 229910003472 fullerene Inorganic materials 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 238000004544 sputter deposition Methods 0.000 claims description 28
- 239000010406 cathode material Substances 0.000 claims description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910014158 LiMn2-x Inorganic materials 0.000 claims 1
- 229910014412 LiMn2−x Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 239000011807 nanoball Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910011902 LiFe1-xMxPO4 Inorganic materials 0.000 description 1
- 229910010595 LiFe1−xMxPO4 Inorganic materials 0.000 description 1
- 229910014169 LiMn2-xMxO4 Inorganic materials 0.000 description 1
- 229910014435 LiMn2−xMxO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 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
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
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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
- 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
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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
- H01M4/48—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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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Abstract
The invention discloses a double-layer coating modified lithium ion battery anode material powder and a preparation method thereof. Wherein the first layer of carbon nanosphere coating is prepared by a wet dispersion-sintering method; the second layer of metal oxide coating is prepared by a magnetron sputtering method, and finally the carbon nanosphere/metal oxide double-layer coating is formed. The double-layer coating layer effectively solves the problem of poor conductivity of the single-layer metal oxide coating, and simultaneously prevents a small amount of HF in circulating electrolyte from corroding the anode material, so that the anode material coated by the double-layer coating layer has high rate capability, high specific capacity and good circulating performance; meanwhile, the method is simple, easy to operate and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a layered transition metal oxide ternary cathode material, and particularly relates to a double-coating-layer modified lithium ion battery cathode material powder and a preparation method thereof.
Background
With the rapid change of portable electronic devices and the accelerated popularization of new energy electric vehicles, lithium ion batteries with higher energy density and power density are required. However, the energy density of a lithium ion battery is largely determined by the cathode material. Among all positive electrode materials, ternary layered LiNixCoyMn1-x-yO2The material has the advantages of high capacity, low cost, low toxicity and the like, and becomes a positive electrode material with great potential.
However, the multi-layered positive electrode material LiNixCoyMn1-x-yO2The defects of low capacity retention rate, quick voltage attenuation, poor rate capability and the like in the circulation process limit the commercial application of the composite material, particularly in the field of new energy power automobiles. The reasons for this are the following:
1. the lithium-containing compound is easy to remain after the surface of the nickel-rich ternary laminar positive electrode material with high specific discharge capacity is sintered; the residual lithium compound is easy to react with carbon dioxide in the air and water to generate Li2CO3And LiOH, and affect the performance of the battery;
2. in the circulation process, trace HF in the electrolyte corrodes the surface of the anode material, so that metal ions are dissolved and the circulation performance of the battery is attenuated;
3. the cycle process of the nickel-rich ternary cathode material leads to further deepening of the lithium-nickel mixed-discharging degree, and the crystal structure of the material is accompanied by a layered structure
To spinel structure
Transforming;
4. the lithium intercalation/deintercalation behavior during the charge and discharge cycle of the material causes the expansion or contraction of the crystal structure of the material, and the subsequent microscopic stress causes the destruction of the material structure and the generation of microcracks.
The surface of the anode material is coated and modified, so that the dissolution of metal ions and the irreversible phase change of the structure caused by the corrosion of HF on the anode can be effectively prevented, and the high-activity Ni can be prevented in the state of high delithiation of the material4+Side reactions with the electrolyte and the precipitation of lattice oxygen inside the material.
In general, metal oxide coating has been shown to be effective in improving the surface stability of the battery material, thereby improving the cycling performance of the battery. But the insulating metal oxide coating causes a decrease in the capacity of the battery.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a double-layer coating modified lithium ion battery anode material powder and a preparation method thereof. The double-layer coated modified lithium ion battery cathode material simultaneously shows high capacity, long cycle and high rate characteristics, has good conductivity, higher surface coverage rate and excellent chemical stability, and can effectively improve the cycle and rate performance of the cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a double-layer coating modified lithium ion battery anode material powder comprises an anode material substrate, a first coating layer coated on the surface of the anode material substrate and a second coating layer coated on the surface of the first coating layer; wherein the first coating layer is a carbon nanosphere coating layer; the second cladding layer is a metal oxide coating.
Preferably, the carbon nanosphere coating three-dimensional material adopts at least one of acetylene black, graphene and multi-wall fullerene. More preferably a multi-walled fullerene.
Preferably, the material of the metal oxide coating adopts at least one of aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, tungsten oxide and zirconium oxide. More preferably at least one of alumina, zirconia and titania.
Preferably, the thickness of the carbon nanoball coating is 2-50 nm, and the particle size of the carbon nanoball is 5-100 nm. More preferably 8-20 nm.
Preferably, the thickness of the metal oxide coating is 2-50 nm. More preferably 5-30nm, most preferably 8-20 nm.
Preferably, the preparation method of the metal oxide coating includes, but is not limited to, any one method of vacuum evaporation deposition, magnetron sputtering deposition, pulsed laser deposition, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam epitaxy deposition and atomic layer deposition.
Preferably, the carbon nanoball coating is prepared by a wet dispersion-sintering method.
Preferably, the metal oxide coating is prepared by a magnetron sputtering method.
Preferably, the molecular formula of the material of the cathode material matrix is Li1+xNiyCozMnsMnO2-rWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, and r is more than or equal to 0 and less than or equal to 0.1.
In addition, preferably, the molecular formula of the material of the cathode material matrix is LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5.
Also preferably, the molecular formula of the material of the cathode material matrix is LiFe1-xMxPO4Wherein x is more than or equal to 0 and less than or equal to 1.
Preferably, the molecular formula of the material of the cathode material matrix is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiFePO4、LiMn2O4At least one of (1). Most preferably LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One kind of (1).
The invention relates to a preparation method of double-layer coating modified lithium ion battery anode material powder, which comprises the following steps:
the method comprises the following steps: the mass ratio of the carbon nanospheres to the positive electrode material matrix is (0.1-5.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally putting the dried product into a muffle furnace, and sintering for 3-10 hours at the temperature of 200-450 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating;
step two: placing the lithium ion battery anode material powder coated with the carbon nanosphere coating prepared in the step one in a magnetron sputtering coating device, enabling the lithium ion battery anode material powder to be in a motion state through a regularly vibrating sample disc, controlling the temperature to be 25-400 ℃ under the pressure condition that the air pressure is 0.1-5.0 Pa, and enabling the power density to be 1-6W/cm2And placing the mixture in an argon gas-oxygen volume ratio of (1-4): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 5-15 min, and obtaining the double-layer coating modified lithium ion battery anode material powder.
Preferably, in the first step, the mass ratio of the carbon nanospheres to the cathode material substrate is (0.5-2.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally placing the dried product into a muffle furnace, and sintering for 5-8 hours at the temperature of 250-400 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating. Effectively improving the bonding force of the carbon nanospheres and the aggregate.
Preferably, in the second step, the motion state is that the cathode material coated with the carbon nanoball moves by at least one of vibration, stirring, rotation and turning. The object is to keep the uncoated side of the material in the plasma, preferably vibrating.
Preferably, in the second step, the temperature is controlled to be 200-400 ℃ under the pressure condition that the air pressure is 0.5-2.0 Pa, and the power density is 2-5W/cm2And placing the mixture in an argon gas-oxygen volume ratio of (2-3): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 8-12 min.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. according to the invention, the conductive carbon nanosphere coating and the metal oxide coating are coated on the surface of the anode material substrate in sequence through a two-step method, wherein the carbon nanosphere coating has good conductivity, and after coating, the conductivity of the composite coating can be integrally improved, electron transmission is promoted, and the rate capability of the material is improved; the metal oxide coating has stable chemical properties, can inhibit side reactions between the electrolyte and the surface of the matrix after coating, optimizes the interface electrochemical reaction environment and improves the cycle performance of the material;
2. the second layer of metal oxide coating is coated by using a magnetron sputtering method, so that the problem that the performance of the material is reduced due to the fact that transition metal elements in the ternary cathode material are easily reduced by a carbon material in the traditional process of preparing the metal oxide coating by high-temperature sintering is solved;
3. the double-coated coating prepared by the process method has good conductivity, higher surface coverage rate and excellent chemical stability, and can effectively improve the cycle and rate performance of the anode material.
Drawings
Fig. 1 is a graph comparing cycle performance curves of the positive electrode materials of example 1 of the present invention and comparative examples 1 and 2.
Fig. 2 is a graph comparing rate performance curves of the positive electrode materials of example 1 of the present invention and comparative examples 1 and 2.
Fig. 3 is a comparison of XRD patterns of the positive electrode materials of example 1 of the present invention and comparative example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1
In this embodiment, a double-layer coating modified lithium ion battery cathode material powder includes a cathode material substrate, a first coating layer coated on the surface of the cathode material substrate, and a second coating layer coated on the surface of the first coating layer; wherein the first coating layer is a carbon nanosphere coating layer; the second cladding layer is a metal oxide coating.
A preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of aluminum oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material coated by the double-layer coating, and the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50mL of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function and enables the material to be in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to 350 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 10sccm oxygen and 25sccm argon, setting the deposition pressure to be 1Pa, opening a radio frequency power supply, and setting the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Example 2
This embodiment is substantially the same as the first embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of zirconia coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, and the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50mL of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2)On a sample table of the magnetron sputtering device, the sample table has a vibration function, so that the powder is in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 400 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 10sccm of oxygen and 40sccm of argon, setting the deposition pressure to be 1.3Pa, and opening a radio frequency power supply to set the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Example 3
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of titanium oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, wherein the specific implementation steps are as follows:
(1) weighing 0.05g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50ml of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 300 ℃ for 5h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function so as to enable the material powder to be in a motion state; vacuumizing the sample cavity of the magnetron sputtering device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 400 ℃; the baffle is closed, and argon is introduced into the reactor at 30sccm, the pre-sputtering power is 100W, the pre-sputtering pressure is 0.8Pa, and the pre-sputtering time is 20 min; opening a baffle plate, respectively introducing 20sccm oxygen and 40sccm argon, setting the deposition pressure to be 1.4Pa, and opening a radio frequency power supply to set the power density to be 4W/cm2And sputtering for 10min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Comparative example 1
Taking the ternary material LiNi in example 10.5Co0.2Mn0.3O2But without any coating treatment.
Comparative example 2
The preparation process of example 1 is repeated except that coating of the carbon nanoball coating is not performed:
(1) the uncoated positive electrode material LiNi0.5Co0.2Mn0.3O2The sample table is placed on a sample table of a magnetron sputtering machine, and the sample table has a vibration function and can enable the powder to be in a motion state;
(2) vacuumizing until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to 350 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min;
(3) opening a baffle plate, respectively introducing 10sccm oxygen and 25sccm argon, setting the deposition pressure to be 1Pa, opening a radio frequency power supply, and setting the power density to be 5W/cm2Sputtering for 10min, wherein the thickness of the deposited metal oxide coating is about 10nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
Electrical performance tests were performed on example 1 and comparative examples 1 and 2, wherein a lithium sheet was used as a negative electrode, positive electrode material powders prepared respectively were used as positive electrodes, a button cell was manufactured in an argon-filled glove box, and charging and discharging were performed at 0.1C and 1C in a voltage range of 2.75 to 4.3V, respectively, and the test results are shown in fig. 1 and 2.
As can be seen from the results of fig. 1, example 1 has the best capacity retention rate in the cycle test with the magnification of 1C, the capacity retention rate after 100 cycles is 79%, while comparative examples 1 and 2 are 43% and 65%, respectively, which shows that the double-layer coating treatment significantly improves the cycle performance of the cathode material;
from the results of fig. 2, it is seen that the specific discharge capacity of example 1 at 5C rate is 102mAh/g, while that of comparative examples 1 and 2 are 42mAh/g and 79mAh/g, respectively, in the rate performance test, and it is known that the rate performance of the double-layer coating-coated positive electrode material is the best.
XRD test was performed on example 1 and comparative examples 1 and 2, and the test results are shown in fig. 3.
As can be seen from the results of fig. 3, the XRD test results of example 1 and comparative examples 1 and 2 show that the positions of the diffraction peaks of the three groups of samples are kept consistent, and compared to comparative example 1, there is no new diffraction peak observable in both example 1 and comparative example 2, because the content of the metal oxide coating is too low.
Example 4
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of the double-layer coating layer modified lithium ion battery anode material powder comprises the steps of firstly, using a wet method-sintering process to obtain LiNi serving as a lithium ion battery anode material0.5Co0.2Mn0.3O2The surface is coated with a multi-wall fullerene coating, and then a layer of titanium oxide coating is coated by a radio frequency sputtering method to prepare the lithium ion battery anode material powder coated by the double-layer coating, wherein the specific implementation steps are as follows:
(1) weighing 0.1g of multi-wall fullerene, uniformly dispersing the multi-wall fullerene in 50ml of absolute ethyl alcohol, pouring 5g of anode material powder into the multi-wall fullerene, heating the absolute ethyl alcohol to 80 ℃, and continuously stirring to evaporate the absolute ethyl alcohol to obtain mixed powder;
(2) putting the mixed powder obtained in the step (1) into a muffle furnace, and sintering at 400 ℃ for 8h to prepare multi-wall fullerene coating-coated anode material powder;
(3) placing the positive electrode material powder coated by the multi-wall fullerene coating prepared in the step (2) on a sample table of a magnetron sputtering device, wherein the sample table has a vibration function so as to enable the material powder to be in a motion state; magnetic control sputteringVacuumizing the sample cavity of the injection device until the vacuum in the cavity is less than 5.0 multiplied by 10-4Pa, setting the temperature of the cavity to be 200 ℃; closing the baffle, introducing argon gas of 30sccm, carrying out pre-sputtering with the power of 100W, the pre-sputtering pressure of 0.8Pa and the pre-sputtering time of 20 min; opening a baffle plate, respectively introducing 20sccm oxygen and 40sccm argon, setting the deposition pressure to be 2.0Pa, and opening a radio frequency power supply to set the power density to be 5W/cm2And sputtering for 15min, wherein the thickness of the metal oxide coating continuously deposited on the surface of the multi-wall fullerene coating is 20nm, and finally the double-layer coating coated modified lithium ion battery anode material powder is prepared.
To sum up, in the above embodiment, the preparation method of the lithium ion battery cathode material powder coated with the double-layer coating layer includes that the substrate material is a nickel cobalt lithium manganate ternary cathode, the first coating layer is a conductive carbon nanosphere coating, and the second coating layer is a metal oxide coating. Wherein the first layer of carbon nanosphere coating is prepared by a wet dispersion-sintering method; the second layer of metal oxide coating is prepared by a magnetron sputtering method, and finally the carbon nanosphere/metal oxide double-layer coating is formed. The double-layer coating layer effectively solves the problem of poor conductivity of the single-layer metal oxide coating, and simultaneously prevents a small amount of HF in circulating electrolyte from corroding the anode material, so that the anode material coated by the double-layer coating layer has high rate capability, high specific capacity and good circulating performance; meanwhile, the method of the embodiment is simple, is easy to operate and is suitable for large-scale industrial production.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be replaced with equivalents as long as the object of the present invention is met, and the technical principle and the inventive concept of the present invention are not departed from the scope of the present invention.
Claims (10)
1. The utility model provides a double-deck coating modified lithium ion battery cathode material powder which characterized in that: the anode material comprises an anode material substrate, a first coating layer coated on the surface of the anode material substrate and a second coating layer coated on the surface of the first coating layer; wherein the first coating layer is a carbon nanosphere coating layer; the second cladding layer is a metal oxide coating.
2. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the carbon nanosphere coating three-dimensional material adopts at least one of acetylene black, graphene and multi-wall fullerene;
or the material of the metal oxide coating adopts at least one of aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, tungsten oxide and zirconium oxide.
3. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the thickness of the carbon nanosphere coating is 2-50 nm, and the particle size of the carbon nanosphere is 5-100 nm.
4. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the thickness of the metal oxide coating is 2-50 nm.
5. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the preparation method of the metal oxide coating comprises but is not limited to any one method of vacuum evaporation deposition, magnetron sputtering deposition, pulsed laser deposition, chemical vapor deposition, metal organic chemical vapor deposition, molecular beam epitaxy deposition and atomic layer deposition;
or, the carbon nanosphere coating is prepared by a wet dispersion-sintering method;
or the metal oxide coating is prepared by a magnetron sputtering method.
6. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the above-mentionedThe molecular formula of the material of the anode material matrix is Li1+xNiyCozMnsMnO2-rWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, and r is more than or equal to 0 and less than or equal to 0.1;
or the molecular formula of the material of the anode material matrix is LiMn2-x’Mx’O4Wherein x' is more than or equal to 0 and less than or equal to 0.5;
or the molecular formula of the material of the anode material substrate is LiFe1-x”Mx”PO4Wherein x is more than or equal to 0 and less than or equal to 1.
7. The double-layer coating layer modified lithium ion battery cathode material powder of claim 1, which is characterized in that: the molecular formula of the material of the anode material matrix is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiFePO4、LiMn2O4At least one of (1).
8. The preparation method of the double-layer coating layer modified lithium ion battery cathode material powder of claim 1 is characterized by comprising the following steps:
the method comprises the following steps: the mass ratio of the carbon nanospheres to the positive electrode material matrix is (0.1-5.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally putting the dried product into a muffle furnace, and sintering for 3-10 hours at the temperature of 200-450 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating;
step two: placing the lithium ion battery anode material powder coated with the carbon nanosphere coating prepared in the step one in a magnetron sputtering coating device, enabling the lithium ion battery anode material powder to be in a motion state through a regularly vibrating sample disc, controlling the temperature to be 25-400 ℃ under the pressure condition that the air pressure is 0.1-5.0 Pa, and enabling the power density to be 1-6W/cm2And are arranged in parallel toThe volume ratio of argon to oxygen is (1-4): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 5-15 min, and obtaining the double-layer coating modified lithium ion battery anode material powder.
9. The preparation method of the double-layer coating layer modified lithium ion battery anode material powder according to claim 8, characterized by comprising the following steps: in the first step, the mass ratio of the carbon nanospheres to the cathode material substrate is (0.5-2.0): dispersing 100 carbon nanospheres in absolute ethyl alcohol, adding the anode material powder, continuously stirring at the temperature of not less than 80 ℃ until the organic solvent is completely evaporated, finally placing the dried product into a muffle furnace, and sintering for 5-8 hours at the temperature of 250-400 ℃ in the air atmosphere to prepare the lithium ion battery anode material powder coated with the carbon nanosphere coating.
10. The preparation method of the double-layer coating layer modified lithium ion battery anode material powder according to claim 8, characterized by comprising the following steps: in the second step, the motion state is that the positive electrode material coated by the carbon nanospheres moves in at least one mode of vibration, stirring, rotation and turning;
or in the second step, under the pressure condition of 0.5-2.0 Pa, the temperature is controlled to be 200-400 ℃, and the power density is 2-5W/cm2And placing the mixture in an argon gas-oxygen volume ratio of (2-3): 1, coating a metal oxide coating on the surface of the anode material under the condition that the sputtering time is 8-12 min.
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