CN115072703A - Composite negative electrode material and preparation method and application thereof - Google Patents
Composite negative electrode material and preparation method and application thereof Download PDFInfo
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- CN115072703A CN115072703A CN202210923355.2A CN202210923355A CN115072703A CN 115072703 A CN115072703 A CN 115072703A CN 202210923355 A CN202210923355 A CN 202210923355A CN 115072703 A CN115072703 A CN 115072703A
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- negative electrode
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- tungstate
- tungsten
- silver
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 239000004332 silver Substances 0.000 claims abstract description 18
- UYKQQBUWKSHMIM-UHFFFAOYSA-N silver tungsten Chemical compound [Ag][W][W] UYKQQBUWKSHMIM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 18
- 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
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000000151 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
- 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 16
- 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
- 239000000203 mixture Substances 0.000 claims description 8
- 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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 1
- 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 17
- 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
- 239000002002 slurry Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 241001226615 Asphodelus albus Species 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 239000003575 carbonaceous 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
- 230000005611 electricity Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 238000005253 cladding Methods 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
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 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
- 239000012528 membrane Substances 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
- 238000013031 physical testing Methods 0.000 description 1
- 230000010287 polarization Effects 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
- 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
Images
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
- H01M4/36—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
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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
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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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- 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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- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a composite negative electrode material and a preparation method and application thereof, belonging 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 using 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 vapor 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 hard carbon of the inner core is improved and the impedance is reduced by means of the advantages of high specific capacity and low electronic impedance of tungsten oxide.
Description
Technical Field
The invention relates to a composite negative electrode material and a preparation method and application thereof, belonging to the technical field of batteries.
Background
The lithium ion battery is more and more widely applied and has good application prospect in a plurality of fields such as electric vehicles and the like. However, with the wider and wider application fields, the performance requirements of different application fields on lithium ion batteries are higher and higher. At present, lithium iron phosphate, ternary materials and the like are mainly used as anode materials of lithium ion batteries, but graphite materials are mainly used as cathode materials. There are also many new types of negative electrode materials, but they have not been applied on a large scale due to various defects.
The hard carbon material is applied to the lithium ion battery by the advantages of large interlayer spacing, good quick charge performance, low expansion, excellent low-temperature performance, wide material source and the like, but the energy density and the first efficiency of the material are low due to large specific surface area and high porosity of the hard carbon.
The measures for increasing the energy density of the hard carbon material mainly include doping phosphorus and silicon elements to increase the energy density and the first efficiency. However, these doping methods also have the problems of large polarization of the cell, high voltage plateau, and low effective first efficiency. The reason is that the porous structure of the hard carbon material causes poor electronic conductivity of the material, which leads to high battery plateau, and one of the measures for improving the electronic impedance of the material is to dope the metal powder with high electronic conductivity to fill in the pores, thereby reducing the occurrence of side reactions and improving the electronic conductivity of the material.
If the metal materials such as silver, copper, tungsten and the like are used as materials with low electronic impedance, if solid phase or liquid phase is adopted for mixing and doping in hard carbon, the problems of material agglomeration and the like can be caused due to the high specific surface area of metal powder, and finally prepared particles are uneven and have poor cycle performance.
Disclosure of Invention
The invention provides a composite negative electrode material, and a preparation method and application thereof, which are used for improving the uniformity and the cycle performance of a hard carbon negative electrode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a 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; 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 using 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 vapor is at least one of concentrated nitric acid and hydrofluoric acid.
In the step 1), the mass ratio of the resin precursor to the tungsten salt to the additive is 100: 1-10: 0.5-2.
The resin precursor in the step 1) is water-based resin.
The step 1) of uniformly mixing the resin precursor, the tungstate and the additive in the water is to uniformly mix the tungstate and the water, then add the resin precursor and uniformly mix the tungstate and the water, and then add the additive and uniformly mix the tungstate and the water. And uniformly mixing tungstate with water to obtain a tungstate solution, wherein the mass fraction of the tungstate solution is 1-10%.
The temperature of the vacuum coating is 200- -2 Pa. During vacuum coating, a silver rod is used as a target material. The vacuum coating time is 10-60 min.
And 3) in the step 3), acid vapor is obtained by mixing and evaporating hydrofluoric acid and concentrated nitric acid. In the acid vapor, the volume ratio of hydrofluoric acid vapor to concentrated nitric acid vapor is 1: 1.
A composite negative electrode material prepared by the preparation method.
A 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.
A sodium 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 beneficial effect 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 hard carbon of the inner core is improved and the impedance is reduced by means of the advantages of high specific capacity and low electronic impedance of tungsten oxide.
2) Further, this application relies on the low advantage of silver self electronic impedance to promote its power performance at granule outer cladding porous silver, and porous silver has high specific surface area and promotes the speed of inserting and taking off of lithium ion, and then promotes the power performance.
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 solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
The starting materials used in the following examples are all commercially available products, unless otherwise specified. The water-based epoxy resin is water-based bisphenol A epoxy resin. The epoxy equivalent weight is 300-400.
The waterborne acrylic resin is styrene acrylic copolymer with molecular weight of 19000-30000.
The molecular weight of the waterborne 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 water-based epoxy resin into 100mL of a 5% iron tungstate aqueous solution by mass, uniformly mixing, then adding 1g of an aluminum-zirconium coupling agent, uniformly mixing, then carrying out spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) depositing a 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) in a vacuum chamber, taking a silver rod as a target material, and performing vacuum deposition at 300 ℃ and under the vacuum degree of 5 multiplied by 10 -2 Carrying out vacuum coating silver plating under the condition of Pa, wherein the deposition rate is 10rpm, and the deposition time is 30min, so as to obtain a silver-tungsten coated carbon precursor;
3) placing the silver-tungsten coated carbon precursor prepared in the step 2) in an evaporating dish, introducing mixed steam of hydrofluoric acid and concentrated nitric acid, and 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 Is 1: 1. The mixed gas can be obtained by mixing hydrofluoric acid and concentrated nitric acid in a mass ratio of 1:1 and then heating to 100 ℃.
The composite negative electrode 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 water-based acrylic resin into 100mL of 1% sodium tungstate aqueous solution by mass fraction, uniformly mixing, then adding 0.5g of aluminum-zirconium coupling agent, uniformly mixing, then carrying out spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) depositing a 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) in a vacuum chamber, taking a silver rod as a target material, and performing vacuum deposition at 200 ℃ and a vacuum degree of 1 multiplied by 10 -2 Pa conditionCarrying out vacuum coating silver plating, wherein the deposition rate is 5rpm, and the deposition time is 60min, so as to obtain a silver-tungsten coated carbon precursor;
3) placing the silver-tungsten coated carbon precursor prepared in the step 2) in an evaporation dish, introducing mixed steam of hydrofluoric acid and concentrated nitric acid, and etching at 80 ℃ for 120min to obtain the silver-tungsten coated carbon precursor. HF and NO in mixed steam of hydrofluoric acid and concentrated nitric acid 2 Is 1: 1. Specifically, the mixed gas is obtained by mixing hydrofluoric acid and concentrated nitric acid in a mass ratio of 1:1 and then heating to 100 ℃.
The composite negative electrode 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 waterborne polyurethane resin into 100mL of aqueous solution of ammonium tungstate with the mass fraction of 10%, uniformly mixing, then adding 2g of aluminum-zirconium coupling agent, uniformly mixing, then carrying out spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) depositing a 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) in a vacuum chamber, taking a silver rod as a target material, and performing vacuum deposition at 500 ℃ and under the vacuum degree of 10 multiplied by 10 -2 Carrying out vacuum coating silver plating under the condition of Pa, wherein the deposition rate is 20rpm, and the deposition time is 10min, so as to obtain a silver-tungsten coated carbon precursor;
3) placing the silver-tungsten coated carbon precursor prepared in the step 2) in an evaporating dish, 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 Is 1: 1. Specifically, hydrofluoric acid and concentrated nitric acid are mixed according to the mass ratio of 1:1 and then heated to 100 ℃ to obtain mixed gas.
The composite negative electrode material for the lithium ion battery of the embodiment is prepared by the method.
Comparative example
The preparation method of the composite negative electrode material for the lithium ion battery of the comparative example comprises the following steps:
1) adding 100g of water-based epoxy resin into 100mL of a 5% iron tungstate aqueous solution by mass, uniformly mixing, then adding 1g of an aluminum-zirconium coupling agent, uniformly mixing, then carrying out spray drying to obtain precursor powder, and briquetting the powder to obtain a precursor block;
2) and (2) placing the precursor block prepared in the step 1) in a tube furnace, heating to 900 ℃ in an argon atmosphere, preserving heat for 3 hours, then cooling to room temperature in the argon atmosphere, and crushing to obtain the precursor block.
The composite anode material for a lithium ion battery of the present comparative example was prepared by the above method.
Examples of the experiments
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 between 3 and 10 μm.
2) Physical and chemical testing
The composite negative electrode materials prepared in the examples 1-3 and the comparative example were tested for particle size D50, tap density, specific surface area and particle size according to the national standard GBT-243354-. The results are shown in Table 1.
TABLE 1 comparison of results of physicochemical tests
As can be seen from table 1, the composite anode material of the present application has uniform particles, small particle size, large tap density, and very large specific surface area.
3) Electricity withholding test
The composite negative electrode materials obtained in examples 1 to 3 and comparative example were used as negative electrode active materials in terms of negative electrode active material, CMC, SBR, SP, H 2 And uniformly mixing the materials according to the mass ratio of the O to the O of 95:2.5:1.5:1:150, mixing the slurry, coating the slurry on a negative current collector, drying and slicing to obtain the negative plate. Then taking the lithium plate as a positive plateThe electrolyte adopts 1mol/L LiPF 6 The solvent is a mixture obtained by mixing EC and DEC according to the volume ratio of 1: 1. The diaphragm adopts a composite film of Polyethylene (PE), polypropylene (PP) and polyethylene propylene (PEP).
A button cell is assembled in an argon-filled glove box, the electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charge-discharge voltage range is controlled to be 0.005-2.0V, and the charge-discharge multiplying power is 0.1C. The button cells finally assembled are marked a1, a2, A3, a4, a5 and B, respectively. And simultaneously testing the specific capacity of the battery under 2C rate discharge, calculating the rate performance (2C/0.1C), and testing the cycle performance.
TABLE 2 comparison of electrochemical Performance test results
As can be seen from table 1, the composite negative electrode material of the present application has a higher specific capacity and a higher first efficiency, because the lithium storage performance of the material is improved by doping tungsten in the material, and the impedance is reduced by doping silver, thereby improving the first efficiency of the material. The outer layer is coated with porous silver, and the power performance of the silver is improved by virtue of the advantage of low electronic impedance of the silver.
4) Pouch cell testing
The composite negative electrode materials obtained in examples 1 to 3 and comparative example were used as negative electrode active materials in terms of negative electrode active material, CMC, SBR, SP, H 2 And uniformly mixing the materials according to the mass ratio of the O to the O of 95:2.5:1.5:1:150, mixing the slurry, coating the slurry on a negative current collector, drying and slicing to obtain the negative plate.
The liquid absorption and retention capacity of the negative electrode sheet is tested according to the national standard GBT-243354 and 2019 graphite cathode materials of lithium ion batteries, and the results are shown in Table 3.
TABLE 3 liquid intake and retention Capacity comparison
And uniformly mixing the NCM523 ternary material serving as the positive active material according to the mass ratio of 95:3:2:100 of the positive active material to the polyvinylidene fluoride to the positive conductive agent to the polyvinylpyrrolidone, mixing the slurry, coating the slurry on a positive current collector, drying and slicing to obtain the positive plate.
The electrolyte adopts 1mol/L LiPF 6 The solvent is a mixture obtained by mixing EC, DEC and PC according to the volume ratio of 1:1: 1. The septum used was Celgard 2400 membrane.
The 5Ah pouch cells were assembled in an argon filled glove box and the final assembled button cells were labeled C1, C2, C3, C4, C5 and D, respectively. The electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, and the cycle performance of the battery under 2C rate charging and 2C rate discharging is tested. The results are shown in Table 4.
TABLE 4 comparison of cycle performance
As can be seen from table 4, the cycling performance of the pouch cells in examples 1-3 are all significantly better than the comparative example, the analytical reasons may be: 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 insertion and the desorption of lithium ions, and the cycle performance of the material is improved.
Claims (10)
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 using 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 vapor is at least one of concentrated nitric acid and hydrofluoric acid.
2. The preparation method of the composite anode material according to claim 1, wherein the mass ratio of the resin precursor, the tungsten salt and the additive in the step 1) is 100: 1-10: 0.5-2.
3. The method for preparing the composite anode material according to claim 1, wherein the resin precursor in the step 1) is an aqueous resin.
4. The preparation method of the composite anode material according to claim 3, wherein the step 1) of uniformly mixing the resin precursor, the tungstate and the additive in water is to uniformly mix the tungstate and the water, add the resin precursor and uniformly mix the tungstate and the water, and then add the additive and uniformly mix the tungstate and the water.
5. The preparation method of the composite anode material according to claim 4, wherein tungstate is uniformly mixed with water to obtain a tungstate solution, and the mass fraction of the tungstate solution is 1-10%.
6. The method for preparing the composite negative electrode material as claimed in claim 1, wherein the temperature of the vacuum coating is 200 ℃ and 500 ℃ and the vacuum degree is 1-10 x 10 -2 Pa。
7. The method for preparing the composite negative electrode material according to claim 6, wherein the time for vacuum coating is 10 to 60 min.
8. The method for preparing the composite anode material according to claim 1, wherein the acid vapor in the step 3) is obtained by mixing and evaporating hydrofluoric acid and concentrated nitric acid.
9. A composite anode material produced by the production method according to claim 1.
10. The application of the composite negative electrode material according to claim 9 in lithium ion batteries or sodium ion batteries, wherein the lithium ion batteries or the sodium ion batteries comprise a positive electrode, a negative electrode, a separator and an electrolyte, 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 material, and the negative electrode active material is the composite negative electrode material according to claim 9.
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