CN115072703B - Composite anode material and preparation method and application thereof - Google Patents
Composite anode material and preparation method and application thereof Download PDFInfo
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- CN115072703B CN115072703B CN202210923355.2A CN202210923355A CN115072703B CN 115072703 B CN115072703 B CN 115072703B CN 202210923355 A CN202210923355 A CN 202210923355A CN 115072703 B CN115072703 B CN 115072703B
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- 239000010405 anode material Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- UYKQQBUWKSHMIM-UHFFFAOYSA-N silver tungsten Chemical compound [Ag][W][W] UYKQQBUWKSHMIM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 150000003657 tungsten Chemical class 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 12
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000006183 anode active material Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 11
- 239000007791 liquid phase Substances 0.000 abstract description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003658 tungsten compounds Chemical class 0.000 abstract description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 10
- 239000007833 carbon precursor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 241001226615 Asphodelus albus Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- 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
- C23C14/24—Vacuum evaporation
-
- 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
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a composite anode material, a preparation method and application thereof, and belongs to the technical field of lithium ion/sodium ion batteries. The preparation method of the composite anode material comprises the following steps: 1) Uniformly mixing a resin precursor, tungsten salt and an additive in water, spray-drying, and briquetting to obtain a precursor block; 2) Depositing a silver film on the surface of the precursor block prepared in the step 1) by utilizing a vacuum coating method to obtain a silver-tungsten coated precursor; 3) Etching the silver-tungsten coated precursor prepared in the step 2) in acid steam at 80-120 ℃ for 30-120min to obtain the silver-tungsten coated precursor; the acid steam is at least one of concentrated nitric acid and hydrofluoric acid. According to the method, the tungsten compound is doped in the hard carbon through a liquid phase method, and the energy density of the core hard carbon is improved and the impedance is reduced by virtue of the advantages of high specific capacity and low electronic impedance of tungsten oxide.
Description
Technical Field
The invention relates to a composite anode material, a preparation method and application thereof, and belongs to the technical field of batteries.
Background
The lithium ion battery is widely applied, and has good application prospect in various fields such as electric vehicles and the like. However, as application fields become wider, performance requirements of lithium ion batteries for different application fields become higher and higher. At present, the positive electrode material of the lithium ion battery mainly adopts lithium iron phosphate, ternary materials and the like, but the negative electrode material mainly adopts graphite materials. There are also various new negative electrode materials, but they have not been applied on a large scale due to various drawbacks.
The hard carbon material is applied to the lithium ion battery by the advantages of large interlayer spacing, good quick charge performance, excellent low expansion and low temperature performance, wide material source and the like, but the energy density and the first efficiency of the material are low due to the large specific surface area and high porosity of the hard carbon.
The measures for improving the energy density of the hard carbon material mainly comprise doping phosphorus and silicon elements to improve the energy density and the first efficiency. However, these doping approaches also have the problems of greater polarization of the cell, higher voltage plateau, and lower effective first efficiency. The reason is mainly that the porous structure of the hard carbon material causes poor electronic conductivity of the material to make the battery platform of the material become high, and one of measures for improving the electronic impedance of the material is to dope metal powder with high electronic conductivity into pores, so that side reactions are reduced and the electronic conductivity of the material is improved.
The metal materials such as silver, copper, tungsten and the like are used as a material with low electronic impedance, for example, solid phase or liquid phase is mixed and doped in hard carbon, and the problems of material agglomeration and the like can be caused due to the high specific surface area of metal powder, so that the finally prepared particles are uneven and have poor cycle performance.
Disclosure of Invention
The invention provides a composite anode material, a preparation method and application thereof, which are used for improving the uniformity and the cycle performance of a hard carbon anode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a composite anode material comprises the following steps:
1) Uniformly mixing a resin precursor, tungsten salt and an additive in water, spray-drying, and briquetting to obtain a precursor block; the resin precursor is at least one of epoxy resin, acrylic resin and polyurethane resin; the tungsten salt is at least one of sodium tungstate, iron tungstate, ammonium tungstate, calcium tungstate and tungsten tetrachloride; the additive is an aluminum zirconium coupling agent;
2) Depositing a silver film on the surface of the precursor block prepared in the step 1) by utilizing a vacuum coating method to obtain a silver-tungsten coated precursor;
3) Etching the silver-tungsten coated precursor prepared in the step 2) in acid steam at 80-120 ℃ for 30-120min to obtain the silver-tungsten coated precursor; the acid steam is at least one of concentrated nitric acid and hydrofluoric acid.
In the step 1), the mass ratio of the resin precursor, the tungsten salt and the additive is 100:1-10:0.5-2.
The resin precursor in step 1) is an aqueous resin.
In the step 1), the resin precursor, the tungstate and the additive are uniformly mixed in water, namely, the tungstate and the water are uniformly mixed first, then the resin precursor is added to be uniformly mixed, and then the additive is added to be uniformly mixed. The tungstate is uniformly mixed with water to obtain a tungstate solution, and the mass fraction of the tungstate solution is 1-10%.
The temperature of the vacuum coating is 200-500 ℃, and the vacuum degree is 1-10 multiplied by 10 -2 Pa. During vacuum coating, silver rods are used as target materials. The vacuum coating time is 10-60min.
The acid steam in the step 3) is obtained by mixing and evaporating hydrofluoric acid and concentrated nitric acid. In the acid steam, the volume ratio of hydrofluoric acid steam to concentrated nitric acid steam is 1:1.
The composite anode material prepared by the preparation method.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, the negative electrode material layer comprises a negative electrode active substance, and the negative electrode active substance is the composite negative electrode material.
The sodium ion battery comprises an anode, a cathode, a diaphragm and electrolyte, wherein the cathode comprises a cathode current collector and a cathode material layer arranged on the surface of the cathode current collector, the cathode material layer comprises a cathode active substance, and the cathode active substance is the composite cathode material.
The beneficial effects of this application:
1) According to the method, the tungsten compound is doped in the hard carbon through a liquid phase method, and the energy density of the core hard carbon is improved and the impedance is reduced by virtue of the advantages of high specific capacity and low electronic impedance of tungsten oxide.
2) Furthermore, the porous silver is coated on the outer layer of the particle, the power performance of the porous silver is improved by virtue of the low electronic impedance of the silver, and the porous silver has a high specific surface area to improve the rate of intercalation and deintercalation of lithium ions, so that the power performance is improved.
Drawings
Fig. 1 is an SEM image of the composite anode material of example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention easier to understand, the invention is described in detail below with reference to specific embodiments.
The raw materials used in the following examples are all commercially available products, except for the specific descriptions. The aqueous epoxy resin is aqueous bisphenol A epoxy resin. The epoxy equivalent is 300-400.
The water-based acrylic resin is styrene acrylic copolymer with a molecular weight of 19000-30000.
The molecular weight of the aqueous polyurethane resin is 10000-40000.
The aluminum-zirconium coupling agent is LD-139 aluminum-zirconium coupling agent.
Example 1
The preparation method of the composite anode material for the lithium ion battery comprises the following steps:
1) Adding 100g of aqueous epoxy resin into 100mL of an aqueous solution of iron tungstate with the mass fraction of 5%, uniformly mixing, adding 1g of aluminum zirconium coupling agent, uniformly mixing, spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) Depositing silver film on the surface of the precursor block by adopting a vacuum coating method, specifically, placing the precursor block prepared in the step 1) into a vacuum chamber, taking a silver rod as a target material, and performing vacuum degree of 5 multiplied by 10 at 300 DEG C -2 Silver plating by a vacuum plating method under the Pa condition, wherein the deposition rate is 10rpm, and the deposition time is 30min, so as to obtain a carbon precursor coated by silver and tungsten;
3) Placing the silver-tungsten coated carbon precursor prepared in the step 2) into an evaporation pan, then introducing mixed steam of hydrofluoric acid and concentrated nitric acid, and then etching at 100 ℃ for 60min to obtain the silver-tungsten coated carbon precursor. HF and NO in mixed steam of hydrofluoric acid and concentrated nitric acid 2 The volume ratio of (2) is 1:1. The mixed gas can be obtained by mixing hydrofluoric acid and concentrated nitric acid according to a mass ratio of 1:1 and heating to 100 ℃.
The composite anode material for the lithium ion battery of the embodiment is prepared by the method.
Example 2
The preparation method of the composite anode material for the lithium ion battery comprises the following steps:
1) Adding 100g of aqueous acrylic resin into 100mL of 1% sodium tungstate aqueous solution, uniformly mixing, adding 0.5g of aluminum-zirconium coupling agent, uniformly mixing, spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) Depositing silver film on the surface of the precursor block by adopting a vacuum coating method, specifically, placing the precursor block prepared in the step 1) into a vacuum chamber, taking a silver rod as a target material, and performing vacuum degree of 1 multiplied by 10 at 200 DEG C -2 Silver plating by a vacuum plating method under the Pa condition, wherein the deposition rate is 5rpm, and the deposition time is 60min, so as to obtain a carbon precursor coated by silver and tungsten;
3) Placing the silver-tungsten coated carbon precursor prepared in the step 2) into an evaporation pan, then introducing mixed steam of hydrofluoric acid and concentrated nitric acid, and then etching for 120min at 80 ℃ to obtain the silver-tungsten coated carbon precursor. HF and NO in mixed steam of hydrofluoric acid and concentrated nitric acid 2 The volume ratio of (2) is 1:1. Specifically, it isAnd mixing hydrofluoric acid and concentrated nitric acid according to a mass ratio of 1:1, and heating to 100 ℃ to obtain the mixed gas.
The composite anode material for the lithium ion battery of the embodiment is prepared by the method.
Example 3
The preparation method of the composite anode material for the lithium ion battery comprises the following steps:
1) Adding 100g of aqueous polyurethane resin into 100mL of aqueous solution of ammonium tungstate with the mass fraction of 10%, uniformly mixing, adding 2g of aluminum-zirconium coupling agent, uniformly mixing, spray-drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) Depositing silver film on the surface of the precursor block by adopting a vacuum coating method, specifically, placing the precursor block prepared in the step 1) into a vacuum chamber, taking a silver rod as a target material, and performing vacuum degree of 10 multiplied by 10 at 500 DEG C -2 Silver plating by a vacuum plating method under the Pa condition, wherein the deposition rate is 20rpm, and the deposition time is 10min, so as to obtain a carbon precursor coated by silver and tungsten;
3) Placing the silver-tungsten coated carbon precursor prepared in the step 2) into an evaporation pan, then introducing mixed steam of hydrofluoric acid and concentrated nitric acid, and then etching for 30min at 120 ℃ to obtain the silver-tungsten coated carbon precursor. HF and NO in mixed steam of hydrofluoric acid and concentrated nitric acid 2 The volume ratio of (2) is 1:1. Specifically, hydrofluoric acid and concentrated nitric acid are mixed according to a mass ratio of 1:1 and then heated to 100 ℃ to obtain mixed gas.
The composite anode material for the lithium ion battery of the embodiment is prepared by the method.
Comparative example
The preparation method of the composite anode material for the lithium ion battery of the comparative example comprises the following steps:
1) Adding 100g of aqueous epoxy resin into 100mL of an aqueous solution of iron tungstate with the mass fraction of 5%, uniformly mixing, adding 1g of aluminum zirconium coupling agent, uniformly mixing, spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) And (3) placing the precursor block prepared in the step (1) in a tube furnace, heating to 900 ℃ under argon atmosphere, preserving heat for 3 hours, cooling to room temperature under argon atmosphere, and crushing to obtain the product.
The composite anode material for lithium ion batteries of the comparative example was prepared by the above method.
Experimental example
1) SEM test
The composite anode material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from FIG. 1, the composite anode material prepared by the invention has a granular structure, and the grain diameter is 3-10 mu m.
2) Physicochemical testing
The composite anode materials prepared in examples 1-3 and comparative example were tested for particle size D50, tap density, specific surface area and particle size according to the national standard GBT-24533-2019 lithium ion battery graphite anode material. The results are shown in Table 1.
Table 1 comparison of physicochemical test results
As can be seen from table 1, the composite anode material of the present application has uniform particles, smaller particle diameter, large tap density, and very large specific surface area.
3) Buckling test
The composite anode materials prepared in examples 1 to 3 and comparative example were taken as anode active materials, according to anode active materials, CMC, SBR, SP, H 2 And uniformly mixing the materials according to the mass ratio of O of 95:2.5:1.5:1:150, mixing the materials, coating the mixture on a negative electrode current collector, drying, and slicing to obtain the negative electrode plate. Then lithium sheets are used as positive electrode sheets, and LiPF with the electrolyte of 1mol/L is adopted 6 The solution, wherein the solvent is a mixture obtained by mixing EC and DEC according to a volume ratio of 1:1. The diaphragm adopts a composite film of polyethylene PE, polypropylene PP and polyethylene propylene PEP.
The button cell is assembled in a glove box filled with argon, the electrochemical performance is carried out on a Wuhan blue electric CT2001A type cell tester, the charging and discharging voltage range is controlled to be 0.005-2.0V, and the charging and discharging multiplying power is controlled to be 0.1C. The final assembled button cells are labeled A1, A2, A3, A4, A5, and B, respectively. Meanwhile, the specific capacity of the battery 2C under the rate discharge was tested, and the rate performance (2C/0.1C) was calculated, and the cycle performance thereof was tested.
Table 2 comparison of electrochemical Performance test results
As can be seen from table 1, the composite anode material of the present application has higher specific capacity and first efficiency, because the lithium storage performance of the material is improved by tungsten doping in the material, and the doped silver doping reduces the impedance, thereby improving the first efficiency of the material. The porous silver is coated on the outer layer, and the power performance of the silver is improved by virtue of the low electronic impedance of the silver.
4) Soft package battery test
The composite anode materials prepared in examples 1 to 3 and comparative example were taken as anode active materials, according to anode active materials, CMC, SBR, SP, H 2 And uniformly mixing the materials according to the mass ratio of O of 95:2.5:1.5:1:150, mixing the materials, coating the mixture on a negative electrode current collector, drying, and slicing to obtain the negative electrode plate.
The liquid absorption and retention capacities of the negative electrode plates were tested according to the national standard GBT-24533-2019 lithium ion battery graphite negative electrode materials, and the results are shown in Table 3.
Table 3 liquid absorbing and retaining ability comparison
And uniformly mixing an NCM523 ternary material serving as a positive electrode active material, polyvinylidene fluoride, a positive electrode conductive agent and polyvinylpyrrolidone according to the mass ratio of 95:3:2:100, mixing the materials, coating the mixture on a positive electrode current collector, drying, and slicing to obtain the positive electrode plate.
The electrolyte adopts LiPF of 1mol/L 6 The solution, wherein the solvent is a mixture obtained by mixing EC, DEC, PC according to a volume ratio of 1:1:1. The membrane was a Celgard 2400 membrane.
The 5Ah pouch cells were assembled in an argon filled glove box, and the final assembled coin cells were labeled C1, C2, C3, C4, C5 and D, respectively. Electrochemical performance was performed on a wuhan blue electric CT2001A battery tester to test the cycling performance of the battery under 2C rate charge and 2C rate discharge. The results are shown in Table 4.
Table 4 cycle performance comparison
As can be seen from table 4, the cycle performance of the soft pack batteries in examples 1 to 3 is significantly better than that of the comparative example, and the analysis may be as follows: the hard carbon composite material with large specific surface area can be prepared by adopting a vacuum coating method, and the structure of the material is stable, so that the cycle performance of the material is improved; meanwhile, the porous silver of the shell is beneficial to the intercalation and deintercalation of lithium ions, and the cycle performance of the material is improved.
Claims (8)
1. The preparation method of the composite anode material is characterized by comprising the following steps of:
1) Uniformly mixing a resin precursor, tungsten salt and an additive in water, spray-drying, and briquetting to obtain a precursor block; the resin precursor is at least one of epoxy resin, acrylic resin and polyurethane resin; the tungsten salt is at least one of sodium tungstate, iron tungstate, ammonium tungstate, calcium tungstate and tungsten tetrachloride; the additive is an aluminum zirconium coupling agent;
2) Depositing a silver film on the surface of the precursor block prepared in the step 1) by utilizing a vacuum coating method to obtain a silver-tungsten coated precursor;
3) Etching the silver-tungsten coated precursor prepared in the step 2) in acid steam at 80-120 ℃ for 30-120min to obtain the silver-tungsten coated precursor; the acid steam is at least one of concentrated nitric acid and hydrofluoric acid;
in the step 1), the mass ratio of the resin precursor, the tungsten salt and the additive is 100:1-10:0.5-2;
the temperature of the vacuum coating is 200-500 ℃, and the vacuum degree is (1-10) multiplied by 10 -2 Pa。
2. The method for producing a composite anode material according to claim 1, wherein the resin precursor in step 1) is an aqueous resin.
3. The method for preparing the composite anode material according to claim 2, wherein in the step 1), the resin precursor, the tungstate and the additive are uniformly mixed in water, wherein the tungstate and the water are uniformly mixed, the resin precursor is added, the resin precursor is uniformly mixed, and the additive is added.
4. The method for preparing the composite anode material according to claim 3, wherein the tungstate is uniformly mixed with water to obtain a tungstate solution, and the mass fraction of the tungstate solution is 1-10%.
5. The method for preparing a composite anode material according to claim 1, wherein the time of vacuum coating is 10-60min.
6. The method for producing a composite anode material according to claim 1, wherein the acid vapor in step 3) is obtained by evaporating hydrofluoric acid and concentrated nitric acid in a mixed manner.
7. A composite anode material produced by the production method according to claim 1.
8. Use of the composite anode material according to claim 7 in a lithium ion battery or a sodium ion battery, the lithium ion battery or the sodium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, the negative electrode comprising a negative electrode current collector and an anode material layer arranged on the surface of the negative electrode current collector, the anode material layer comprising an anode active material, characterized in that the anode active material is the composite anode material according to claim 7.
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