CN116759550A - Coating modification method for lithium ion battery oxide positive electrode material, composite material and application thereof - Google Patents
Coating modification method for lithium ion battery oxide positive electrode material, composite material and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002715 modification method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 90
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 67
- 239000000956 alloy Substances 0.000 claims abstract description 67
- 238000000498 ball milling Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000005300 metallic glass Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims 1
- 238000005275 alloying Methods 0.000 claims 1
- 239000002103 nanocoating Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000000875 high-speed ball milling Methods 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 36
- 239000010949 copper Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 18
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 16
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910001092 metal group alloy Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/626—Metals
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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Abstract
The application discloses a coating modification method of an oxide positive electrode material of a lithium ion battery, a composite material and application thereof, and belongs to the field of lithium ion battery materials. The coating modification method is characterized in that the characteristic of high forming capacity of zirconium-based metallic glass components is utilized, an amorphous structure can be maintained or crystalline alloy can be rapidly amorphized in the process of wet ball milling with oxide anode material powder, nano-scale coating of the zirconium-based amorphous alloy on oxide anode material particles is realized by virtue of a softening layer according to the characteristic of shearing and softening of a surface layer of the zirconium-based amorphous alloy under the mechanical action of high-speed ball milling, the conductivity of the material is improved while the surface protection is provided, and the generation of mechanical processing microcracks is inhibited, so that the cycle stability of the whole composite material is ensured. The regulation and control of the thickness of the coating layer within 3-30 nanometers are realized by adjusting the components and the particle size of the metal glass, so that the performance of the anode material is further optimized. The application has the advantages of simple operation, adjustable composition of the coating layer, wide composition range and the like.
Description
Technical Field
The application relates to a coating modification method of an oxide positive electrode material of a lithium ion battery and a composite material thereof, belonging to the field of lithium ion battery materials.
Background
The development of various portable electronic devices, the rising of industries such as electric automobiles, green electricity energy storage and the like, has put higher demands on the performance of lithium ion batteries, particularly on the energy density. The oxide positive electrode material is a key for improving the energy density of the lithium ion battery, and the improvement of the working voltage is helpful for improving the energy density, but the related capacity attenuation problem is a main reason for slow commercialization process of the high-capacity and high-voltage positive electrode material.
The capacity decay of the positive electrode material is closely related to the failure behavior of the positive electrode material, and the failure behavior of the positive electrode material tends to occur on the surface firstly, wherein the failure behavior comprises side reaction with electrolyte, desolventizing of transition metal ions and irreversible transformation to a cubic structure; microcracks also develop inside the crystal during high charge-discharge pressures or cycles, and the newly formed crack surfaces then undergo a similar failure process, resulting in accelerated capacity decay. Thus, researchers have attempted to eliminate the capacity fade effect of the positive electrode material by surface cladding.
At present, the coating materials of the positive electrode materials of the lithium ion batteries mainly comprise pure metals, inorganic nonmetallic materials and high polymer materials. Pure metal coating has obvious advantages in mechanical property, conductivity and the like, but is easy to oxidize or react with oxide at high temperature or high energy, and is difficult to form a uniform and compact coating layer; inorganic nonmetallic outlets, particularly common oxide coating, are common methods in commercial production, but cannot fundamentally solve the problems of high interface impedance and easy crack generation in electrode plate rolling processing; common anode material coating technologies such as high-temperature sintering and vapor deposition cannot be used for coating and modifying the surface of the anode material by the polymer material.
Metallic glass is a structurally disordered alloy formed by cooling and freezing an alloy melt. When the temperature rises to the glass transition temperature T g (well below the alloy melting point) into the supercooled liquid region, viscosity and shear modulus drop sharply, and deformation behavior similar to plastic softening occurs. The metal glass has many different physical and chemical characteristics with crystalline metal materials, has ultrahigh corrosion resistance, no intergranular corrosion, good wettability with oxide, oxidation resistance and can effectively block the diffusion of oxygen in the oxide to the coating layer. Among the metallic glass materials, zirconium-based metallic glass has a large forming ability, and the main constituent elements of zirconium and aluminum are doping elements beneficial to the electrochemical stability of the oxide cathode material. The application provides a method for coating an oxide positive electrode material by using a zirconium-based metallic glass alloy, which successfully realizes a zirconium-based amorphous nanoscale coating layer of the oxide positive electrode material at room temperature by wet ball milling and provides a new way and method for coating modification of the oxide positive electrode material.
Disclosure of Invention
Aiming at the problems existing in the prior art, the application provides a method for coating the lithium ion battery oxide positive electrode material by utilizing the superplastic deformation capability of the zirconium-based metallic glass alloy, thereby realizing the nano coating modification of the zirconium-based amorphous alloy.
In order to achieve the above purpose, the application adopts the following technical scheme:
the coating modification method of the lithium ion battery oxide cathode material is a wet ball milling method of zirconium-based metal glass coated oxide, and comprises the following steps:
firstly, adding zirconium-based metallic glass alloy powder and oxide powder into a ball milling tank according to a certain proportion, adding a ball milling medium according to a certain mass ratio, adding a solvent according to a certain volume ratio, and then sealing the ball milling tank.
Secondly, placing the ball milling tank in a ball mill, and performing wet ball milling according to a certain ball milling speed and ball milling time.
And finally, after ball milling, filtering the slurry in a ball milling tank, drying at 80-120 ℃ for 3-15 hours to obtain powder, and sieving the powder to obtain the zirconium-based metal glass coated oxide positive electrode material.
Further, the zirconium-based metallic glass powder alloy powder is powder particles of zirconium-based alloy with large amorphous forming capacity, the granularity is not more than 50 microns, and the basic component is Zr x TM y Al 1-x-y Wherein, TM is one or more than one of Fe, co, ni, cu, wherein, x is more than or equal to 50 and less than or equal to 70, and preferably, x is more than or equal to 55 and less than or equal to 65; y is more than or equal to 15 and less than or equal to 35, preferably y is more than or equal to 20 and less than or equal to 30; zr in the basic component can be partially replaced by Ti and Nb, and the replaced atomic percentage cannot exceed 20% of the whole alloy; other metal elements (Mn, sn, ag, zn) can be added to the basic component of the component to form metal microalloying, and the atomic content of the other metal elements is generally not more than 5% of the whole alloy.
Further, the oxide powder comprises a layered positive electrode material system and a high-voltage positive electrode material system, wherein the layered positive electrode material system is LiNi x Co y Mn 1-x-y O 2 (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), and the high-voltage positive electrode material system is LiMn 2 O 4 、LiNi 0.5 Mn 1.5 O 4 . The particle size of the oxide powder ranges from 0.3 to 10 microns.
Further, the weight ratio of the zirconium-based metallic glass alloy to the oxide material is 50:1-10:1, preferably 40:1-25:1.
Further, the weight ratio of the ball milling medium to the two powder samples is 2:1-25:1, preferably 10:1-20:1.
Further, the ball milling medium is a grinding ball, and the diameter range of the ball milling medium is 0.5 mm-15 mm, preferably 0.8 mm-5 mm.
Further, the solvent is water or ethanol or a mixture of the water and the ethanol; the volume of the solvent accounts for 20-80% of the volume fraction of the ball milling tank, preferably 45-70%.
Further, the ball milling speed is 200-550 rpm, preferably 300-450 rpm; the total time of the ball milling is 2 to 20 hours, preferably 5 to 9 hours.
Further, the sieving size was 300 mesh.
The lithium ion battery oxide positive electrode material is prepared by adopting the coating modification method, the thickness of an amorphous alloy coating layer is 3-30 nanometers, and the thickness of the coating layer can be regulated and controlled by adjusting alloy components and particle sizes.
The application of the lithium ion battery oxide positive electrode material is that the lithium ion battery oxide positive electrode material is used as an electrode material for a lithium ion battery.
The principle of the application is as follows:
(1) The application mainly uses the characteristic of large glass forming capability of zirconium-based metallic glass alloy components, and maintains an amorphous structure in the ball milling process or enables crystalline alloy to be rapidly amorphized in the ball milling process. By utilizing the characteristic that the surface layer of the zirconium-based amorphous alloy is sheared and softened under the mechanical action of high-speed ball milling, the nano-scale coating of the zirconium-based amorphous alloy on the oxide positive electrode material particles is realized by means of the softening layer, the conductivity of the material is improved while the surface protection is provided, and the generation of mechanical processing microcracks is inhibited, so that the circulation stability of the whole composite material is ensured.
(2) The lower the melting point of the zirconium-based metallic glass alloy component is, the lower the glass transition temperature is, the surface shear softening is more easily generated, and the generated nano coating layer is thicker; the smaller the alloy powder particles are, the higher the coating efficiency is, and the thicker the nano coating layer is. Therefore, the thickness of the coating layer can be regulated and controlled by adjusting the alloy composition and the particle size.
The beneficial effects of the application are as follows:
(1) The compact coating of the zirconium-based metallic glass alloy on the oxide can be realized;
(2) The process is simple, the operation is simple, complex equipment is not needed, and the large-scale preparation is easy to realize;
(3) The coating layer has adjustable components and wide component range;
(4) The thickness of the coating layer is adjustable;
(5) The coating layer has metal conductivity, and is beneficial to improving the low-temperature conductivity of the positive electrode material.
Drawings
FIG. 1 is Zr prepared in example 1 56 Co 26 Al 15 Mn 2 Ag 3 Scanning electron microscope pictures of metal glass powder.
FIG. 2 is Zr prepared in example 1 56 Co 26 Al 15 Mn 2 Ag 3 XRD pattern of metallic glass powder.
Fig. 3 is an XRD pattern of the original lithium cobaltate and the coated lithium cobaltate in example 1.
Fig. 4 is an HRTEM image of the lithium cobaltate coated in example 1.
FIG. 5 is a graph showing the electrochemical cycle performance of the original lithium cobalt oxide and the coated lithium cobalt oxide in example 1.
FIG. 6 is Zr prepared in example 2 60 Nb 10 Cu 15 Ni 5 Al 10 XRD pattern of crystalline alloy powder.
Fig. 7 is an XRD pattern of the original lithium manganese nickelate and the coated lithium manganese nickelate in example 2.
Fig. 8 is an HRTEM image of the lithium manganese nickel oxide coated in example 2.
FIG. 9 is a graph comparing electrochemical cycling performance of the original lithium manganese nickelate and the coated lithium manganese nickelate of example 2.
Detailed Description
The specific shaping process and effect of the application are further illustrated by two specific examples.
EXAMPLE 1Zr 56 Co 26 Al 15 Mn 2 Ag 3 Metallic glass coated layered lithium cobalt oxide (LiCoO) 2 ) Positive electrode material
Step one, preparing Zr 56 Co 28 Al 18 Metal glass powder
Taking high-purity Zr (99.9%), co (more than 99.9%), al (99.9%), mn (99%), ag (99.9%) as raw materials, weighing and preparing the atomic percentage composition of Zr 56 Co 26 Al 15 Mn 2 Ag 3 Is a metal alloy. 100 g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then vacuumized to 1 x 10 -4 The arc melting is carried out by charging 500mbar high-purity Ar gas (99.9%) for four times, each time for 3 minutes, and an alloy spindle is obtained.
The master alloy ingot is crushed and then is put into powder making equipment, under the atmosphere of Ar, the master alloy is heated to a molten state through high-frequency induction smelting, then a spray switch is started, molten metal liquid passes through high-pressure Ar gas, the alloy liquid is atomized by the high-pressure gas, powder is formed after cooling, and finally, the powder with the particle size of less than 50 mu m is screened by a screen and is collected. Characterizing the powder shape by adopting a Scanning Electron Microscope (SEM), and confirming that the spherical powder has regular shape and most of the powder has a micron-sized diameter (figure 1); the phase structure of the powder is characterized by an X-ray diffractometer (XRD) (figure 2), no sharp crystal diffraction peak exists in the spectrum, and only diffuse reflection peaks for representing amorphous characteristics appear, so that the powder is a metallic glass amorphous alloy.
Step two, preparing a metallic glass coated lithium cobalt oxide material
Taking 0.5 g of zirconium-based metallic glass powder obtained in the previous step and 10 g of commercial lithium cobalt oxide powder (LiCoO) with the particle size of 1-5 microns 2 99%, microphone), the two materials were simply mixed and poured into a 250 ml tank of ni Long Qiumo, 50g of 10 mm diameter zirconia balls, 50g of 5mm diameter zirconia balls and 50g of 2 mm diameter zirconia balls were added, and then 120 ml of absolute ethanol was added; ball milling was performed using a planetary ball mill at 300rpm, each ball milling was suspended for 10 minutes every 50 minutes, repeated 6 times, and the ball milling product was filtered through a 300 mesh stainless steel screen, and then subjected to a ball milling at 90 ℃And drying for 10 hours to obtain the lithium cobaltate material powder. The XRD pattern of the obtained material was consistent with that of commercial lithium cobalt oxide (fig. 3), indicating that the metal alloy therein was present in an amorphous state. High Resolution Transmission Electron Microscopy (HRTEM) characterization (as shown in fig. 4) shows that the metallic glass forms an amorphous coating of about 6 nm on the surface of lithium cobaltate.
Mixing metallic glass coated lithium cobalt oxide, acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with the diameter of 12 mm, wherein the lithium metal plate is used as a counter electrode and 1mol/L LiPF is used as a counter electrode 6 And (3) assembling a CR2032 button battery by using an (EC+DEC) electrolyte (volume ratio of 1:1) as the electrolyte and Celgard 2300 as a diaphragm in a glove box filled with argon, and performing electrochemical test at room temperature after taking out. The battery has a charge-discharge voltage range of 2.5-4.5V, a primary charge capacity of 181mAh/g, a discharge capacity of 160mAh/g, and a reversible capacity of 145mAh/g after 35 cycles, and capacities of 173mAh/g, 145mAh/g and 121mAh/g corresponding to commercial lithium cobaltate under the same conditions.
EXAMPLE 2Zr 60 Nb 10 Cu 15 Ni 5 Al 10 Metallic glass coated high pressure lithium manganese nickel (LiNi) 0.5 Mn 1.5 O 4 ) Positive electrode material
Step one, preparing Zr 65 Cu 15 Ni 10 Al 10 Crystalline alloy powder
Taking high-purity Zr (99.9%), nb (99.9%), cu (more than 99.9%), ni (more than 99.9%) and Al (99.9%) metal particles as raw materials, weighing and preparing the Zr as atomic percentage components 60 Nb 10 Cu 15 Ni 5 Al 10 Is a metal alloy. 50g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then the mixture is vacuumized to 1 x 10 -4 The arc melting is carried out by charging 500mbar high-purity Ar gas (99.9%) for four times each for 2 minutes, and an alloy spindle is obtained.
The master alloy ingot is crushed and then is put into powder making equipment, under the atmosphere of Ar, the master alloy is heated to a molten state through high-frequency induction smelting, then a spray switch is started, molten metal liquid passes through high-pressure Ar gas, the alloy liquid is atomized by the high-pressure gas, powder is formed after cooling, and finally, the powder with the particle size of less than 50 mu m is screened by a screen and is collected. The collected powder was heated to 600 c at 5 degrees per minute in an argon atmosphere tube furnace, kept warm for half an hour and then air cooled to room temperature. XRD characterization (fig. 6) was performed on the obtained powder, and the spectrum showed sharp diffraction peaks, confirming that the powder material was crystalline.
Step two, preparing a metal glass coated lithium manganese nickelate material
Taking 0.5 g of the crystalline alloy powder obtained in the last step and 10 g (LiNi) of commercial lithium manganese nickel oxide powder with the particle size of 0.3-2 microns 0.5 Mn 1.5 O 4 99%, clamar), the two materials are simply mixed and poured into a 250 ml tank of a Ni Long Qiumo tank, 55 g of 10 mm diameter zirconia balls, 55 g of 5mm diameter zirconia balls and 60 g of 2 mm diameter zirconia balls are added, and then 150 ml of absolute ethyl alcohol is added; ball milling is carried out by using a planetary ball mill at a rotating speed of 250rpm, 5 minutes are paused every 55 minutes of ball milling, the ball milling is repeated for 12 times, and after the ball milling product is filtered by a 300-mesh stainless steel screen, the ball milling product is dried for 5 hours at 110 ℃ to obtain the lithium manganese nickel oxide material powder. The XRD pattern of the obtained material was consistent with that of commercial lithium manganese nickel oxide (fig. 7), indicating that the metal alloy therein was present in an amorphous state. HRTEM characterization of the material showed (fig. 8) that the alloy formed an amorphous coating of about 10 nm on the lithium manganese nickel surface.
Mixing metallic glass coated lithium nickel manganese oxide, acetylene black and PVDF according to a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with a diameter of 12 mm, wherein the lithium metal plate is used as a counter electrode, and 1mol/L LiPF is used as a counter electrode 6 the/(EC+DMC) electrolyte (volume ratio 1:1) is electrolyte, celgard 2300 is diaphragm, and the CR2032 button cell is assembled in a glove box filled with argon, and electrochemical test is carried out at room temperature after the cell is taken out. Under the conditions that the charge-discharge voltage range of the battery is 3-5V and the current density is 140mA/g (see figure 9), the initial charge capacity is 132mAh/g, the discharge capacity is 131mAh/g, the reversible capacity after 300 times of circulation is 127mAh/g, and the same conditions are adoptedThe capacities of the corresponding commercial lithium nickel manganese oxide are 129mAh/g, 123mAh/g and 118mAh/g respectively.
EXAMPLE 3Zr 55 Ti 12 Cu 12 Ni 6 Al 10 Sn 5 Metallic glass coated NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) Positive electrode material
Step one, preparing Zr 65 Cu 15 Ni 10 Al 10 Crystalline alloy powder
Taking high-purity Zr (99.9%), ti (more than 99.9%), cu (more than 99.9%), ni (more than 99.9%), al (99.9%), sn (99.9%) metal particles as raw materials, weighing and preparing the Zr as atomic percentage components 55 Ti 12 Cu 12 Ni 6 Al 10 Sn 5 Is a metal alloy. 50g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then the mixture is vacuumized to 1 x 10 -4 The arc melting is carried out by charging 500mbar high-purity Ar gas (99.9%) for four times each for 2 minutes, and an alloy spindle is obtained.
The method comprises the steps of crushing a master alloy ingot, loading the crushed master alloy ingot into powder making equipment, heating the master alloy to a molten state through high-frequency induction smelting under the atmosphere of Ar, starting a spray switch to enable molten metal liquid to pass through high-pressure Ar gas, spraying the alloy liquid into mist by utilizing the high-pressure gas, cooling to form powder, and finally screening the powder with the particle size of less than 10 mu m by adopting a screen and collecting the powder. XRD characterization of the obtained powder showed that the powder material was amorphous.
Step two, preparing NCM811 material coated by metal glass
Taking 0.5 g of the crystalline alloy powder obtained in the last step and 10 g of commercial NCM811 powder (LiNi 0.8 Co 0.1 Mn 0.1 O 2 99%, encyclopedia), the two materials were simply mixed and poured into a 250 ml tank of nylon Long Qiumo, 55 g of 10 mm diameter zirconia balls, 55 g of 5mm diameter zirconia balls and 60 g of 2 mm diameter zirconia balls were added, and then 150 ml of water was added; ball milling was performed using a planetary ball mill at 500rpm, 5 minutes were paused every 55 minutes of ball milling, 3 times were repeated, and the ball milled product was treated with 300 mesh stainless steelAfter sieving and filtering, the powder of the coated NCM811 material was obtained by drying at 120℃for 3 hours. The XRD pattern of the obtained material was consistent with that of commercial NCM811, indicating that the metal alloy therein was present in the amorphous state. HRTEM characterization of the material showed that the alloy formed an amorphous coating of about 18 nm on the NCM811 surface.
Mixing a metal glass coated NCM811 material, acetylene black and PVDF in a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with the diameter of 12 mm, wherein a lithium metal plate is used as a counter electrode, and 1mol/L LiPF is used as the counter electrode 6 the/(EC+DMC) electrolyte (volume ratio 1:1) is electrolyte, celgard 2300 is diaphragm, and the CR2032 button cell is assembled in a glove box filled with argon, and electrochemical test is carried out at room temperature after the cell is taken out. Under the conditions of 3-4.5V of charging and discharging voltage and 50mA/g of current density, the initial charging capacity is 203mAh/g, the discharging capacity is 197mAh/g, the reversible capacity after 50 times of circulation is 190mAh/g, and the capacities of corresponding commercial NCM811 under the same conditions are 206mAh/g, 198mAh/g and 179mAh/g respectively.
EXAMPLE 4Zr 56 Co 28 Al 18 Metallic glass coated layered lithium cobalt oxide (LiCoO) 2 ) Positive electrode material
Step one, preparing Zr 56 Co 28 Al 18 Metal glass powder
Taking high-purity Zr (99.9%), co (more than 99.9%) and Al (99.9%) metal particles as raw materials, weighing and preparing the atomic percentage composition of Zr 56 Co 28 Al 18 Is a metal alloy. 100 g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then vacuumized to 1 x 10 -4 The arc melting is carried out by charging 500mbar high-purity Ar gas (99.9%) for five times each for 3 minutes, and the alloy spindle is obtained.
The master alloy ingot is crushed and then is put into powder making equipment, under the atmosphere of Ar, the master alloy is heated to a molten state through high-frequency induction smelting, then a spray switch is started, molten metal liquid passes through high-pressure Ar gas, the alloy liquid is atomized by the high-pressure gas, powder is formed after cooling, and finally, the powder with the particle size of less than 50 mu m is screened by a screen and is collected. Characterizing the powder shape by adopting a Scanning Electron Microscope (SEM), and confirming that the spherical powder has regular shape and most of the powder has micron-sized diameter; the XRD is adopted for characterization, and powder is confirmed to be amorphous alloy in the spectrum.
Step two, preparing a metallic glass coated lithium cobalt oxide material
Taking 0.5 g of zirconium-based metallic glass powder obtained in the previous step and 10 g of commercial lithium cobalt oxide powder (LiCoO) with the particle size of 1-5 microns 2 99% of microphone), the two materials are simply mixed and poured into a 250 ml tank of a Ni Long Qiumo, 50g of zirconia balls with the diameter of 10 mm, 50g of zirconia balls with the diameter of 5mm and 50g of zirconia balls with the diameter of 2 mm are added, and then 120 ml of mixed solution of absolute ethyl alcohol and water is added, wherein the volume ratio of the absolute ethyl alcohol to the water is 1:1; ball milling was performed using a planetary ball mill at 400rpm, each ball milling was suspended for 10 minutes every 50 minutes, repeated 8 times, and the ball milling product was filtered through a 300 mesh stainless steel screen and dried at 80 ℃ for 12 hours to obtain a lithium cobaltate-coated material powder. The XRD pattern of the obtained material is consistent with that of commercial lithium cobalt oxide, which shows that the metal alloy exists in an amorphous state. HRTEM characterization of the material showed that the metallic glass formed an amorphous coating of about 7 nm on the lithium cobaltate surface.
Mixing metallic glass coated lithium cobalt oxide, acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with the diameter of 12 mm, wherein the lithium metal plate is used as a counter electrode and 1mol/L LiPF is used as a counter electrode 6 And (3) assembling a CR2032 button battery by using an (EC+DEC) electrolyte (volume ratio of 1:1) as the electrolyte and Celgard 2300 as a diaphragm in a glove box filled with argon, and performing electrochemical test at room temperature after taking out. Under the conditions of the battery charge-discharge voltage range of 2.5-4.5V and the current density of 50mA/g, the primary charge capacity is 182mAh/g, the discharge capacity is 161mAh/g, the reversible capacity after 35 times of circulation is 147mAh/g, and the capacities of corresponding commercial lithium titanate under the same conditions are 173mAh/g, 145mAh/g and 121mAh/g respectively.
EXAMPLE 5Zr 65 Cu 15 Ni 10 Al 10 Metal glassCoating high-pressure manganese nickel acid lithium (LiNi) 0.5 Mn 1.5 O 4 ) Positive electrode material
Step one, preparing Zr 65 Cu 15 Ni 10 Al 10 Crystalline alloy powder
Taking high-purity Zr (99.9%), cu (more than 99.9%), ni (more than 99.9%) and Al (99.9%) metal particles as raw materials, weighing and preparing the atomic percentage composition of Zr 65 Cu 15 Ni 10 Al 10 Is a metal alloy. 50g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then the mixture is vacuumized to 1 x 10 -4 And (3) charging high-purity Ar gas (99.9%) with the pressure of 500mbar for arc melting, and repeatedly melting for eight times for 2 minutes each time to obtain an alloy spindle.
The master alloy ingot is crushed and then is put into powder making equipment, under the atmosphere of Ar, the master alloy is heated to a molten state through high-frequency induction smelting, then a spray switch is started, molten metal liquid passes through high-pressure Ar gas, the alloy liquid is atomized by the high-pressure gas, powder is formed after cooling, and finally, the powder with the particle size of less than 50 mu m is screened by a screen and is collected. The collected powder was heated to 600 c at 5 degrees per minute in an argon atmosphere tube furnace, kept warm for half an hour and then air cooled to room temperature. XRD characterization is carried out on the obtained powder, and sharp diffraction peaks appear on the spectrum, so that the powder material is proved to be crystalline.
Step two, preparing a metal glass coated lithium manganese nickelate material
Taking 0.5 g of the crystalline alloy powder obtained in the last step and 10 g (LiNi) of commercial lithium manganese nickel oxide powder with the particle size of 0.3-2 microns 0.5 Mn 1.5 O 4 99%, clamar), the two materials are simply mixed and poured into a 250 ml tank of a Ni Long Qiumo tank, 55 g of zirconia balls with the diameter of 12 mm, 55 g of zirconia balls with the diameter of 5mm and 60 g of zirconia balls with the diameter of 1 mm are added, and then 150 ml of absolute ethyl alcohol is added; ball milling is carried out by using a planetary ball mill at a rotating speed of 450rpm, 5 minutes are paused every 55 minutes of ball milling, 3 times are repeated, and after ball milling products are filtered by a 300-mesh stainless steel screen, the products are dried for 3 hours at 120 ℃ to obtain the lithium manganese nickel oxide material powder. The XRD pattern of the obtained material is consistent with that of commercial lithium manganese nickel oxideIndicating that the metal alloy therein exists in an amorphous state. HRTEM characterization of the material showed that the alloy formed an amorphous coating of about 10 nm on the lithium manganese nickelate surface.
Mixing metallic glass coated lithium nickel manganese oxide, acetylene black and PVDF according to a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with a diameter of 12 mm, wherein the lithium metal plate is used as a counter electrode, and 1mol/L LiPF is used as a counter electrode 6 the/(EC+DMC) electrolyte (volume ratio 1:1) is electrolyte, celgard 2300 is diaphragm, and the CR2032 button cell is assembled in a glove box filled with argon, and electrochemical test is carried out at room temperature after the cell is taken out. The battery has a charge-discharge voltage range of 3-5V, a first charge capacity of 133mAh/g, a discharge capacity of 132mAh/g, a reversible capacity of 126mAh/g after 300 times of circulation, and capacities of 129mAh/g, 123mAh/g and 118mAh/g corresponding to commercial lithium titanate under the same conditions.
EXAMPLE 6Zr 65 Cu 15 Ni 10 Al 10 Metallic glass coated NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) Positive electrode material
Step one, preparing Zr 65 Cu 15 Ni 10 Al 10 Crystalline alloy powder
Taking high-purity Zr (99.9%), cu (more than 99.9%), ni (more than 99.9%) and Al (99.9%) metal particles as raw materials, weighing and preparing the atomic percentage composition of Zr 65 Cu 15 Ni 10 Al 10 Is a metal alloy. 50g of raw materials are mixed and placed in a water-cooled copper crucible of a non-consumable arc melting furnace, and then the mixture is vacuumized to 1 x 10 -4 The arc melting is carried out by charging 500mbar high-purity Ar gas (99.9%) for four times each for 2 minutes, and an alloy spindle is obtained.
The method comprises the steps of crushing a master alloy ingot, loading the crushed master alloy ingot into powder making equipment, heating the master alloy to a molten state through high-frequency induction smelting under the atmosphere of Ar, starting a spray switch to enable molten metal liquid to pass through high-pressure Ar gas, spraying the alloy liquid into mist by utilizing the high-pressure gas, cooling to form powder, and finally screening the powder with the particle size of less than 10 mu m by adopting a screen and collecting the powder. XRD characterization of the obtained powder showed that the powder material was amorphous.
Step two, preparing NCM811 material coated by metal glass
Taking 0.5 g of the crystalline alloy powder obtained in the last step and 10 g of commercial NCM811 powder (LiNi 0.8 Co 0.1 Mn 0.1 O 2 99%, encyclopedia), the two materials were simply mixed and poured into a 250 ml tank of nylon Long Qiumo, 55 g of 10 mm diameter zirconia balls, 55 g of 5mm diameter zirconia balls and 60 g of 2 mm diameter zirconia balls were added, and then 150 ml of water was added; ball milling was performed using a planetary ball mill at 500rpm, each ball milling was paused for 5 minutes for 55 minutes, repeated 18 times, and the ball milling product was filtered through a 300 mesh stainless steel screen and dried at 120 ℃ for 3 hours to obtain NCM811 coated material powder. The XRD pattern of the obtained material was consistent with that of commercial NCM811, indicating that the metal alloy therein was present in the amorphous state. HRTEM characterization of the material showed that the alloy formed an amorphous coating of about 15 nm on the NCM811 surface.
Mixing a metal glass coated NCM811 material, acetylene black and PVDF in a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on an aluminum foil, vacuum drying at 120 ℃ for 5 hours, and stamping the slurry into a round electrode plate with the diameter of 12 mm, wherein a lithium metal plate is used as a counter electrode, and 1mol/L LiPF is used as the counter electrode 6 the/(EC+DMC) electrolyte (volume ratio 1:1) is electrolyte, celgard 2300 is diaphragm, and the CR2032 button cell is assembled in a glove box filled with argon, and electrochemical test is carried out at room temperature after the cell is taken out. Under the conditions of 3-4.5V of charging and discharging voltage and 50mA/g of current density, the initial charging capacity is 205mAh/g, the discharging capacity is 198mAh/g, the reversible capacity after 50 times of circulation is 192mAh/g, and the capacities of corresponding commercial lithium titanate under the same conditions are 206mAh/g, 198mAh/g and 179mAh/g respectively.
The examples described above represent only embodiments of the application and are not to be understood as limiting the scope of the patent of the application, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the application, which fall within the scope of protection of the application.
Claims (10)
1. The coating modification method of the lithium ion battery oxide positive electrode material is characterized by comprising the following steps of:
firstly, adding zirconium-based metallic glass alloy powder and oxide powder into a ball milling tank in proportion, adding a ball milling medium and a solvent, and sealing the ball milling tank;
secondly, placing the ball milling tank in a ball mill, and performing wet ball milling according to a certain ball milling speed and ball milling time;
and finally, after ball milling is finished, filtering the slurry in a ball milling tank, drying to obtain powder, and sieving the powder to obtain the zirconium-based metal glass coated oxide positive electrode material.
2. The method for coating and modifying an oxide positive electrode material of a lithium ion battery according to claim 1, wherein the zirconium-based metallic glass powder alloy powder is powder particles of a zirconium-based alloy having a large amorphous forming ability, the particle size is not more than 50 μm, and the base component is Zr x TM y Al 1-x-y Wherein, TM is one or more than one of Fe, co, ni, cu, wherein, x is more than or equal to 50 and less than or equal to 70, and y is more than or equal to 15 and less than or equal to 35.
3. The coating modification method of the lithium ion battery oxide cathode material according to claim 2, wherein Zr in the basic component of the zirconium-based metallic glass powder alloy can be partially replaced by Ti and Nb, and the atomic percentage of the replacement cannot exceed 20% of the whole alloy; in addition, other metal elements can be added for metal micro-alloying, and the atomic content of the other metal elements is not more than 5% of the whole alloy, wherein the other metal elements comprise Mn, sn, ag, zn.
4. The method for coating and modifying an oxide positive electrode material of a lithium ion battery according to claim 2, wherein the base component Zr is as follows x TM y Al 1-x-y In the formula, x is preferably 55-65, and y is preferably 20-30.
5. The method for coating and modifying an oxide positive electrode material of a lithium ion battery according to claim 1, wherein the oxide powder comprises a layered positive electrode material system and a high-voltage positive electrode material system, and the layered positive electrode material system is LiNi x Co y Mn 1-x-y O 2 (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), and the high-voltage positive electrode material system is LiMn 2 O 4 、LiNi 0.5 Mn 1.5 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the oxide powder ranges from 0.3 to 10 microns.
6. The coating modification method of the lithium ion battery oxide positive electrode material according to claim 1, wherein the weight ratio of the zirconium-based metallic glass alloy to the oxide material is 50:1-10:1; the weight ratio of the ball milling medium to the two powder samples is 2:1-25:1; the diameter range of the ball milling medium is 0.5 mm-15 mm; the solvent is water or ethanol or a mixture of the water and the ethanol, and the volume of the solvent accounts for 20-80% of the volume fraction of the ball milling tank; the ball milling speed is 200-550 rpm, and the total ball milling time is 2-20 hours.
7. The method for coating and modifying an oxide positive electrode material of a lithium ion battery according to claim 6, wherein the weight ratio of the zirconium-based metallic glass alloy to the oxide material is preferably 40:1-25:1; the weight ratio of the ball milling medium to the two powder samples is preferably 10:1-20:1; the diameter range of the ball milling medium is preferably 0.8 mm-5 mm; the volume fraction of the solvent in the ball milling tank is preferably 45-70%; the ball milling speed is preferably 300-450 rpm, and the total ball milling time is preferably 5-9 hours.
8. The coating modification method of the lithium ion battery oxide cathode material according to claim 1, wherein the drying temperature is 80-120 ℃ and the drying time is 3-15.
9. The lithium ion battery oxide positive electrode material is characterized in that the coating oxide material is prepared by adopting the coating modification method of any one of claims 1-8, the thickness of an amorphous alloy coating layer is 3-30 nanometers, and the thickness of the coating layer can be regulated and controlled by adjusting alloy components and particle sizes.
10. Use of the lithium ion battery oxide cathode material according to claim 9 as an electrode material for lithium ion batteries.
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| JP2010018878A (en) * | 2008-07-14 | 2010-01-28 | Tohoku Univ | Nano-size metal glass structure |
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| CN107759249A (en) * | 2017-11-20 | 2018-03-06 | 中南大学 | A kind of oxide carbide composite coating containing chromium and preparation method thereof |
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| CN113629254A (en) * | 2021-10-12 | 2021-11-09 | 浙江帕瓦新能源股份有限公司 | Preparation method of single crystal high-nickel low-cobalt or cobalt-free cathode material |
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| JP2010018878A (en) * | 2008-07-14 | 2010-01-28 | Tohoku Univ | Nano-size metal glass structure |
| CN106207128A (en) * | 2016-08-31 | 2016-12-07 | 南开大学 | A kind of Zr (OH)4the preparation method of cladding nickel cobalt aluminum tertiary cathode material |
| CN107759249A (en) * | 2017-11-20 | 2018-03-06 | 中南大学 | A kind of oxide carbide composite coating containing chromium and preparation method thereof |
| CN108258229A (en) * | 2018-01-30 | 2018-07-06 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary electrode of lithium cell of glassy metal base and preparation method |
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