CN114975969A - Sulfur-based multi-metal composite material, preparation, pole piece and lithium ion battery - Google Patents
Sulfur-based multi-metal composite material, preparation, pole piece and lithium ion battery Download PDFInfo
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- CN114975969A CN114975969A CN202210770579.4A CN202210770579A CN114975969A CN 114975969 A CN114975969 A CN 114975969A CN 202210770579 A CN202210770579 A CN 202210770579A CN 114975969 A CN114975969 A CN 114975969A
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- sulfur
- copper
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- aluminum
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 51
- 239000011593 sulfur Substances 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 239000002905 metal composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 111
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 30
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005056 compaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000013122 aluminium-based metal-organic framework Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
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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
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A sulfur-based multi-metal composite material, a preparation method thereof, a pole piece and a lithium ion battery belong to the technical field of lithium ion batteries, and overcome the defects of low specific capacity and low cycle retention rate when the material in the prior art is used as a lithium ion battery cathode material. The preparation method of the sulfur-based multi-metal composite material comprises the following steps: step 1, preparing copper-based MOFs materials and aluminum-based MOFs materials, and adding silicon powder and tungsten powder for doping in the preparation process; step 2, etching the copper-based MOFs material and the aluminum-based MOFs material by adopting a sulfur-based material under an acidic condition to obtain a precursor; step 3, depositing a carbon and fluorine mixed layer on the surface of the precursor; and 4, coating boron oxide on the surface of the product obtained in the step 3. The invention improves the comprehensive performance of the lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a sulfur-based multi-metal composite material, preparation, a pole piece and a lithium ion battery.
Background
The composite lithium ion battery material has the functions of serving as an electron carrier and an ion carrier in the charge and discharge processes of the battery, can release and store energy, has higher specific gravity in the aspect of battery cost composition, and is one of the key components of the lithium ion battery. In a composite lithium ion battery, hard carbon is considered as the most successful anode material for industrial energy storage systems due to its good stability and low voltage. However, the ion deintercalation capacity of hard carbon is not outstanding, and each carbon ring can only intercalate one Li + Formation of LiC6 resulted in its lower theoretical specific capacity (372mAh g) -1 ). In addition, studies have shown that hard carbon has a series of side reactions with the electrolyte to some extent, which affects the cycle performance of the battery and is highly likely to cause a series of safety problems.
The MOFs are the abbreviation of metal-organic framework compounds, and are crystalline porous materials with periodic network structures formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands through self-assembly, and have multiple properties such as porosity, large specific surface area, multiple metal sites and the like. Because of their unique microstructures, MOFs-based materials have begun to open up completely in the electrochemical field.
However, the improvement of the comparative capacity and the cycle retention rate of the conventional MOFs-based material as the lithium ion battery cathode material is limited.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low specific capacity and low cycle retention rate when the material in the prior art is used as a lithium ion battery cathode material, so that the sulfur-based multi-metal composite material, the preparation method, the pole piece and the lithium ion battery are provided.
Therefore, the invention provides the following technical scheme.
In a first aspect, the present invention provides a method for preparing a sulfur-based polymetal composite material, comprising the steps of:
step 1, preparing copper-based MOFs materials and aluminum-based MOFs materials, and adding silicon powder and tungsten powder for doping in the preparation process;
step 2, etching the copper-based MOFs material and the aluminum-based MOFs material by adopting a sulfur-based material under an acidic condition to obtain a precursor;
step 3, depositing a carbon and fluorine mixed layer on the surface of the precursor;
and 4, coating boron oxide on the surface of the product obtained in the step 3.
Further, the step 1 comprises:
(1) mixing 1, 3, 5-pyromellitic acid, a copper source and triethanolamine, and stirring to obtain a first mixed solution;
(2) mixing an aluminum source and terephthalic acid, and stirring to obtain a second mixed solution;
(3) and mixing the first mixed solution, the second mixed solution, the silicon powder and the tungsten powder, heating for reaction, cooling, performing solid-liquid separation, washing and drying a solid product to obtain the mixed material of the Si and W-doped copper-based MOFs material and the aluminum-based MOFs material.
Further, the step 1 satisfies at least one of conditions a to D:
A. the step 1 (1) comprises: mixing 1, 3, 5-pyromellitic acid with a first solvent to obtain a solution A; dissolving a copper source in a second solvent to obtain a solution B, uniformly mixing the solution A and the solution B, adding triethanolamine, and stirring for 1-5 hours;
preferably, the dosage ratio of the 1, 3, 5-pyromellitic acid to the first solvent is (10-20) g: (150- > 200) ml;
preferably, the using ratio of the copper source to the second solvent is (20-30) g: (50-70) ml;
preferably, the mass ratio of the 1, 3, 5-pyromellitic acid to the copper source is (10-20): (20-30);
preferably, the first solvent comprises at least one of DMF and absolute ethanol, and the second solvent is deionized water;
preferably, the copper source comprises at least one of copper nitrate trihydrate or copper acetate monohydrate;
preferably, the molar ratio of the 1, 3, 5-pyromellitic acid to the triethanolamine is (0.4-1): 1;
B. the step 1 (2) comprises: dissolving an aluminum source and terephthalic acid in a third solvent, and stirring for 10-100 min;
preferably, the molar ratio of the aluminium source to the terephthalic acid is 1: (0.5 to 0.8), more preferably 1: 0.6;
preferably, the aluminum source comprises at least one of aluminum nitrate nonahydrate or aluminum isopropoxide;
preferably, the third solvent is deionized water;
preferably, the volume ratio of the sum of the mass of the aluminum source and the mass of the terephthalic acid to the third solvent is (50-150) g/(100-300) ml;
C. in the step (3) of the step 1, the silicon powder and the tungsten powder are in a nanometer level, and the mass ratio of the silicon powder to the copper source is (0.1-5): 20; the mass ratio of the tungsten powder to the copper source is (0.1-5): 20;
D. in the step (3) of the step 1, the heating reaction temperature is 200-220 ℃, and the time is 24-30 h.
Further, the step 2 comprises: and (3) mixing the product obtained in the step (1), a sulfur-based material and a fourth solvent to obtain a third mixed solution, heating and stirring the third mixed solution, filtering and washing the third mixed solution to obtain a precursor.
Further, at least one of the conditions a-F is satisfied:
A. adding hydrogen peroxide while adding a sulfur-based material, wherein the purity of the hydrogen peroxide is 3%, and the volume ratio of the hydrogen peroxide to the fourth solvent is (3-5): (150-300);
B. adjusting the pH value of the third mixed solution to be less than or equal to 1 by using dilute sulfuric acid or oxalic acid;
C. the sulfur-based material is at least one of thioacetamide, sodium thiosulfate or sodium sulfide, and preferably thioacetamide;
D. the heating temperature is 50-60 ℃, the stirring speed is 300-400 r/min, and the stirring time is 15-20 min;
E. the fourth solvent is absolute ethyl alcohol, DMF or isopropanol;
F. the molar weight ratio of the copper source and the aluminum source to the sulfur-based material is (0.6-1.2): 1.
further, the step 3 comprises: introducing carbon tetrafluoride gas, and depositing a uniform carbon and fluorine mixed layer on the surface of the precursor by chemical vapor deposition;
preferably, argon with the volume fraction of 20 percent is added into the carbon tetrafluoride gas as a protective gas;
preferably, the temperature of the chemical vapor deposition is 600-650 ℃;
preferably, the pressure of the chemical vapor deposition is 80-100 Pa;
preferably, the deposition speed of the chemical vapor deposition is 10-15 nm/min;
preferably, the deposition time of the chemical vapor deposition is 10-20 min.
Further, the step 4 comprises: mixing the product obtained in the step (3) with a boron source, and then sintering at high temperature in a protective atmosphere to obtain a product with the surface coated with boron oxide;
preferably, the boron source comprises at least one of boric acid or boron oxide;
preferably, the mass ratio of the boron source to the product in the step 3 is 1 (50-500);
preferably, the product obtained in the step 3 and a boron source are mixed in a mixing tank, the rotating speed during mixing is 150-250 r/min, and the mixing time is 60-90 min;
preferably, the protective atmosphere comprises any one or a combination of two of argon or nitrogen;
preferably, the sintering temperature is 250-350 ℃, and the sintering time is 5-7 h.
In a second aspect, the present invention provides a sulfur-based multi-metallic composite.
In a third aspect, the invention provides a lithium ion battery pole piece, which comprises the sulfur-based polymetallic composite material.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the lithium ion battery pole piece.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of a sulfur-based multi-metal composite material, which comprises the following steps: step 1, preparing copper-based MOFs materials and aluminum-based MOFs materials, and adding silicon powder and tungsten powder for doping in the preparation process; step 2, etching the copper-based MOFs material and the aluminum-based MOFs material by adopting a sulfur-based material under an acidic condition to obtain a precursor; step 3, depositing a carbon and fluorine mixed layer on the surface of the precursor; and 4, coating boron oxide on the surface of the product obtained in the step 3.
According to the sulfur-based polymetallic composite material, a matrix is a mixture of two MOFs materials with different morphologies, wherein the micro morphology of the Cu-based MOFs material is a regular octahedron with the particle size of about 0.3 mu m, the micro morphology of the Al-based MOFs material is a dodecahedron with the particle size of about 0.5 mu m, the powder compaction of the material can be improved by mixing the Cu-based MOFs material and the Al-based MOFs material, the expansion of the material in the charging and discharging process is relieved, and the ionic conductivity of the material can be improved by doping Si and W elements; adding a sulfur-based material under an acidic condition, etching a Cu metal framework in the Cu-based MOFs material and an Al metal framework in the aluminum-based MOFs material, forming pores in a substrate material, introducing a sulfur source, and reacting nano-scale tungsten powder and the sulfur-based material to generate tungsten sulfide so as to improve the capacity exertion and rate capability of the material; the coated carbon and fluorine mixed layer can improve the electronic conductivity of the material, and the carbon and fluorine mixed layer is soft in layer-by-layer texture, so that the influence caused by the volume expansion of the composite material in the charge and discharge processes of the material can be relieved, the corrosion of electrolyte to the interior of the composite material in the use process of the composite material can be reduced, and the rate capability and the cycle performance of the composite material are improved; the finally coated boron oxide can further improve the capacity of the material and improve the cycle performance of the material.
2. The preparation method provided by the invention comprises the following steps of 1: (1) mixing 1, 3, 5-pyromellitic acid, a copper source and triethanolamine, and stirring to obtain a first mixed solution; (2) mixing an aluminum source and terephthalic acid, and stirring to obtain a second mixed solution; (3) and mixing the first mixed solution, the second mixed solution, the silicon powder and the tungsten powder, heating for reaction, cooling, filtering, washing and drying to obtain the mixed material of the Si and W-doped copper-based MOFs material and the aluminum-based MOFs material.
The MOFs material is synthesized by a hydrothermal method, the method is simple, and the raw materials are easy to obtain. The first mixed solution and the second mixed solution are prepared respectively, and then the first mixed solution and the second mixed solution are mixed with the silicon powder and the tungsten powder, so that the silicon powder and the tungsten powder, the copper-based MOFs material and the aluminum-based MOFs material are mixed and grow together, and the structural stability and the ionic conductivity of the product are enhanced.
3. The preparation method provided by the invention comprises the following steps of 4: mixing the product obtained in the step (3) with a boron source, and then sintering at high temperature in a protective atmosphere to obtain a product with the surface coated with boron oxide; the sintering temperature is 250-350 ℃, and the sintering time is 5-7 h. The sintering temperature is low, which not only does not damage the material itself, but also can improve the electrochemical performance of the sample.
4. The sulfur-based multi-metal composite material provided by the invention has Cu-based and Al-based dual-structure MOFs inside, the two MOFs have different appearances, and the mixture of the two MOFs can fill gaps, so that not only can powder compaction be improved, the volume expansion of the material be relieved, but also the electronic conduction distance between the material and the material can be shortened, more contact areas can reduce the internal resistance of the material during multiplying power charging and discharging, and the unique MOFs structure enables the pore diameter to be larger, thereby improving the ionic and electronic conductivity of the battery material; after being etched by a sulfur-based material, a high-capacity sulfur element is introduced, so that the capacity of the composite material can be improved while the material is subjected to pore forming, and the carbon and fluorine mixed layer is uniformly coated outside the composite material, so that the corrosion of the electrolyte to the body is reduced, and the overall circulation stability is improved; the outermost layer is also provided with a nano-grade boron oxide coating layer, so that the capacity is improved, and the cycle performance of the material is improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a sulfur-based multi-metal composite material, and the preparation method comprises the following steps:
step 1, (1) solution 1: weighing 10g of 1, 3, 5-pyromellitic acid, adding the 1, 3, 5-pyromellitic acid into 150mL of mixed solution of DMF and absolute ethyl alcohol (the volume ratio is 1:1), dissolving 20g of copper nitrate trihydrate into 50mL of water, adding 10mL of triethanolamine after the two solutions are uniformly mixed, and stirring the mixed solution for 3 hours for later use.
(2) Solution 2: 75g of aluminum nitrate nonahydrate and 20g of terephthalic acid (molar ratio of the two is 1:06) are weighed respectively, mixed and dissolved in 120mL of deionized water, and stirred for 10 min.
(3) And mixing the solutions 1 and 2, adding 1g of nano silicon powder and 1g of nano tungsten powder, stirring the mixed solution at the rotation speed of 300r/min and the temperature of 45 ℃ for 1h to uniformly disperse the nano silicon powder and the tungsten powder, then placing the mixture in a 500mL reaction kettle, and heating and reacting at 200 ℃ for 24 h. And after the heating reaction is finished, cooling the reaction kettle to room temperature, washing and centrifuging the reaction kettle for 2-3 times respectively by using DMF (dimethyl formamide) and deionized water, and finally drying the reaction kettle in a vacuum drying oven at 60 ℃ for 12 hours to obtain the mixed material of the Si and W-doped copper-based MOFs material and the aluminum-based MOFs material.
And 2, putting the prepared mixed material of the copper-based MOFs material and the aluminum-based MOFs material into a beaker filled with 300ml of absolute ethyl alcohol, adopting dilute sulfuric acid to adjust the pH value of the solution to about 1.0, heating while stirring, controlling the stirring speed to be 300r/min and the temperature to be 50 ℃, adding 60g of sodium thiosulfate and 3ml of hydrogen peroxide with the mass concentration of 3% into the beaker after 10min, continuously stirring for 15min, filtering the solution, washing for a plurality of times by adopting absolute ethyl alcohol, and finally drying for 12h in a blast drying box at 60 ℃ to obtain the mixed precursor material of the copper-based MOFs material and the aluminum-based MOFs material etched by the sulfur-based material.
And 3, putting the precursor material into a chemical vapor deposition instrument, introducing carbon tetrafluoride gas, wherein argon with the volume fraction of 20% is also contained in the carbon tetrafluoride gas as protective gas, controlling the temperature of chemical vapor deposition to be 600 ℃, the pressure to be 80Pa, the deposition speed to be 10nm/min and the deposition time to be 10min, and depositing a uniform carbon and fluorine mixed thin film layer with the thickness of 100nm outside the precursor material.
Step 4, putting the product obtained in the step 3 into a mixing tank, adding 1g of boric acid and a proper amount of zirconium beads (the mass ratio of the boric acid to the product obtained in the step 3 is 1:1), then installing the mixing tank on a planetary mixer, and mixing for 60min at the rotating speed of 200 r/min; and (3) placing the mixed sample in a tube furnace, introducing argon as a protective gas, and sintering at the temperature of 280 ℃ for 5 hours to obtain the final sulfur-based multi-metal composite material.
Example 2
The embodiment provides a sulfur-based multi-metal composite material, and the preparation method comprises the following steps:
step 1, (1) solution 1: 15g of 1, 3, 5-pyromellitic acid is weighed and added into 200mL of a mixed solution of DMF and absolute ethyl alcohol (the volume ratio is 1:1), 25g of copper nitrate trihydrate is dissolved in 50mL of water, 12.5mL of triethanolamine is added after the two solutions are uniformly mixed, and the mixed solution is stirred for 3 hours for later use.
(2) Solution 2: 90g of aluminum nitrate nonahydrate and 24g of terephthalic acid (molar ratio of the two is 1:06) are weighed respectively, mixed and dissolved in 144ml of deionized water, and stirred for 10 min.
(3) And mixing the solutions 1 and 2, adding 1.5g of nano silicon powder and 1.5g of nano tungsten powder, stirring the mixed solution at the rotation speed of 300r/min and the temperature of 45 ℃ for 1h, then placing the mixed solution in a 1000ml reaction kettle, and heating and reacting at 210 ℃ for 26 h. And after the heating reaction is finished, cooling the reaction kettle to room temperature, washing and centrifuging the reaction kettle for 2-3 times respectively by using DMF (dimethyl formamide) and deionized water, and finally drying the reaction kettle in a vacuum drying oven at 60 ℃ for 12 hours to obtain the mixed material of the Si and W-doped copper-based MOFs material and the aluminum-based MOFs material.
And 2, putting the prepared mixed material of the copper-based MOFs material and the aluminum-based MOFs material into a beaker filled with 300ml of absolute ethyl alcohol, adopting dilute sulfuric acid to adjust the pH of the solution to be below 1.0, heating and stirring the solution, controlling the stirring speed to be 300r/min and the temperature to be 50 ℃, adding 30g of thioacetamide and 4ml of hydrogen peroxide with the mass concentration of 3% into the beaker after 10min, continuously stirring the solution for 15min, filtering the solution, washing the solution for a plurality of times by using absolute ethyl alcohol, and finally drying the solution in a blast drying oven at 60 ℃ for 12h to obtain the mixed precursor material of the copper-based MOFs material and the aluminum-based MOFs material etched by the first sulfur source.
3, putting the copper-based MOFs material and the aluminum-based MOFs material mixed material etched by the first sulfur source into a chemical vapor deposition instrument, introducing carbon tetrafluoride gas, wherein the carbon tetrafluoride gas also contains 20% by volume of argon as a protective gas, controlling the temperature of chemical vapor deposition to be 600 ℃, the pressure to be 80Pa, the deposition speed to be 15nm/min and the deposition time to be 14min, and depositing a uniform carbon-fluorine mixed thin film layer with the thickness of 200nm outside the precursor after the deposition is finished;
step 4, putting the sample prepared in the step 3 into a mixing tank, adding 1.5g of boric acid and a proper amount of zirconium beads (the mass ratio of the boric acid to the product in the step 3 is 1:1), then installing the mixing tank on a planetary mixer, and mixing for 75min at the rotating speed of 200 r/min; and (3) placing the mixed sample in a tube furnace, introducing argon as a protective gas, and sintering at the temperature of 330 ℃ for 6h to obtain the final sulfur-based multi-metal composite material.
Example 3
The difference between the embodiment and the embodiment 2 is only that in the step 2, the stirring speed is controlled to be 300r/min, the temperature is controlled to be 60 ℃, 35g of thioacetamide is added into a beaker after 10min, 4ml of hydrogen peroxide is added to accelerate the reaction, and the solution is filtered after stirring for 30 min. Other conditions and parameters were exactly the same as those in example 2.
Example 4
The difference between the embodiment and the embodiment 2 is that in the step 1, the solutions 1 and 2 are mixed, 3g of nano silicon powder and 3g of nano tungsten powder are added, the mixed solution is stirred for 1 hour at the rotating speed of 300r/min and the temperature of 60 ℃, and then is placed in a 1000ml reaction kettle to be heated and reacted for 26 hours at the temperature of 210 ℃. Other conditions and parameters were exactly the same as those in example 2.
Example 5
This example differs from example 2 only in that in step 4, the sample prepared in step 3 is placed in a mixing bowl, 2.5g of boric acid and an appropriate amount of zirconium beads are added, and then the mixing bowl is mounted on a planetary mixer and mixed for 90min at a rotation speed of 200 r/min; and (3) placing the mixed sample in a tube furnace, introducing argon as a protective gas, and sintering at the temperature of 350 ℃ for 8 hours to obtain the final sulfur-based multi-metal composite material. Other conditions and parameters were exactly the same as those in example 2.
Comparative example 1
A conventional silicon carbon anode material (BTR, S400B) was used as a comparative example.
And (3) performance testing:
the sulfur-based multi-metal composite materials obtained in examples 1 to 5 and the material of comparative example 1 were partially tested for physical and chemical properties, and the other part was assembled into a button cell in a glove box, the slurry ratio and the coating thickness were controlled to be the same, and then the electrochemical properties were tested using a blue test system and a Princeton electrochemical workstation, and the electrical and physical and chemical test results are shown in tables 1 and 2:
TABLE 1 Electrical Properties
As can be seen from Table 1, from examples 1 to 5, the specific first discharge capacity of the battery obtained by using the composite material of the present invention was 758.6mAh g -1 Above, the capacity retention rate of 0.1C circulation at normal temperature for 100 weeks can reach more than 60.3 percent, the capacity retention rate of 0.1C circulation at 45 ℃ for 100 weeks can reach more than 55.4 percent, and the 1C discharge specific capacity at normal temperature can reach 612.4 mAh.g -1 Above, the normal temperature 4C specific discharge capacity can reach 448.6mAh g -1 The above. The above electrical property data are significantly better than comparative example 1.
As can be seen from Table 2, from examples 1 to 5, the ion diffusion coefficients of the batteries obtained by using the composite materials of the present inventionD Li + (cm 2 ·s -1 ) Is still at a minimum of 1.04X 10 -10 cm 2 ·s -1 Above, the powder compaction at 2T is 1.34g/cm 3 The specific surface area of the powder was 251.3m 2 (ii) a powder resistivity of 0.204. omega. cm or less. The above physicochemical test data are significantly better than comparative example 1.
The comparison between example 1 and example 2 shows that the synthesis conditions and parameters of example 2 are more suitable for obtaining sulfur-based multi-metal composite materials with more balanced properties.
Compared with the embodiment 2 and the embodiment 3, the addition amount and the etching time of the sulfur-based material can affect the performance of the prepared composite material, and if the addition amount of the sulfur-based material is increased, the capacity exertion (gram capacity) of the material can be obviously improved, the etching time is increased, pores can be further formed, the specific surface area of the material is increased, and the rate capability of the material is improved. However, with the increase of the proportion of the sulfur-based material, the overall particle strength of the composite material is reduced, the compaction of the negative pole piece is reduced, and the energy density of the battery is reduced.
TABLE 2 physicochemical Properties
From the comparison between example 2 and example 4, the addition amount of the nano silicon powder and the nano tungsten powder mainly affects the conductive capability and some electrical properties of the prepared composite material. If the addition amount of the nano silicon powder and the nano tungsten powder is increased, the powder resistivity of the material is reduced, and the ion diffusion capacity of the material is improved, so that the rate capability of the material is improved.
From a comparison of example 2 and example 5, the material according to the invention is coated with borides in the outermost layer for improved interface and increased capacity. If the coating amount of boron is increased, the capacity exertion of the material can be obviously improved, the corrosion of the electrolyte to the material can be reduced, and the cycle retention rate of the material can be improved. However, increasing the amount of boron coating causes a decrease in the specific surface area of the material and a decrease in rate capability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The preparation method of the sulfur-based multi-metal composite material is characterized by comprising the following steps of:
step 1, preparing a copper-based MOFs material and an aluminum-based MOFs material, and adding silicon powder and tungsten powder for doping in the preparation process;
step 2, etching the copper-based MOFs material and the aluminum-based MOFs material by adopting a sulfur-based material under an acidic condition to obtain a precursor;
step 3, depositing a carbon and fluorine mixed layer on the surface of the precursor;
and 4, coating boron oxide on the surface of the product obtained in the step 3.
2. The method of preparing a sulfur-based polymetal composite according to claim 1, wherein said step 1 comprises:
(1) mixing 1, 3, 5-pyromellitic acid, a copper source and triethanolamine, and stirring to obtain a first mixed solution;
(2) mixing an aluminum source and terephthalic acid, and stirring to obtain a second mixed solution;
(3) and mixing the first mixed solution, the second mixed solution, the silicon powder and the tungsten powder, heating for reaction, cooling, performing solid-liquid separation, washing and drying a solid product to obtain the mixed material of the Si and W-doped copper-based MOFs material and the aluminum-based MOFs material.
3. The method for preparing a sulfur-based polymetal composite according to claim 2, wherein said step 1 satisfies at least one of conditions a-D:
A. the step 1 (1) comprises: mixing 1, 3, 5-pyromellitic acid with a first solvent to obtain a solution A; dissolving a copper source in a second solvent to obtain a solution B, uniformly mixing the solution A and the solution B, adding triethanolamine, and stirring for 1-5 hours;
preferably, the dosage ratio of the 1, 3, 5-pyromellitic acid to the first solvent is (10-20) g: (150- > 200) ml;
preferably, the using ratio of the copper source to the second solvent is (20-30) g: (50-70) ml;
preferably, the mass ratio of the 1, 3, 5-pyromellitic acid to the copper source is (10-20): (20-30);
preferably, the first solvent comprises at least one of DMF and absolute ethanol, and the second solvent is deionized water;
preferably, the copper source comprises at least one of copper nitrate trihydrate or copper acetate monohydrate;
preferably, the molar ratio of the 1, 3, 5-pyromellitic acid to the triethanolamine is (0.4-1): 1;
B. the step 1 (2) comprises: dissolving an aluminum source and terephthalic acid in a third solvent, and stirring for 10-100 min;
preferably, the molar ratio of the aluminium source to the terephthalic acid is 1: (0.5 to 0.8), more preferably 1: 0.6;
preferably, the aluminum source comprises at least one of aluminum nitrate nonahydrate or aluminum isopropoxide;
preferably, the third solvent is deionized water;
preferably, the volume ratio of the sum of the mass of the aluminum source and the mass of the terephthalic acid to the third solvent is (50-150) g/(100-300) ml;
C. in the step (3) of the step 1, the silicon powder and the tungsten powder are in a nanometer level, and the mass ratio of the silicon powder to the copper source is (0.1-5): 20; the mass ratio of the tungsten powder to the copper source is (0.1-5): 20;
D. in the step (3) of the step 1, the heating reaction temperature is 200-220 ℃, and the time is 24-30 h.
4. The method of preparing a sulfur-based polymetal composite according to claim 1, wherein said step 2 comprises: and (3) mixing the product obtained in the step (1), a sulfur-based material and a fourth solvent to obtain a third mixed solution, heating and stirring the third mixed solution, filtering and washing the third mixed solution to obtain a precursor.
5. The method for producing a sulfur-based polymetal composite material according to claim 4, wherein at least one of conditions A-F is satisfied:
A. adding hydrogen peroxide while adding a sulfur-based material, wherein the purity of the hydrogen peroxide is 3%, and the volume ratio of the hydrogen peroxide to the fourth solvent is (3-5): (150-300);
B. adjusting the pH value of the third mixed solution to be less than or equal to 1 by using dilute sulfuric acid or oxalic acid;
C. the sulfur-based material is at least one of thioacetamide, sodium thiosulfate or sodium sulfide, and preferably thioacetamide;
D. the heating temperature is 50-60 ℃, the stirring speed is 300-400 r/min, and the stirring time is 15-20 min;
E. the fourth solvent is absolute ethyl alcohol, DMF or isopropanol;
F. the molar weight ratio of the copper source and the aluminum source to the sulfur-based material is (0.6-1.2): 1.
6. the method for preparing a sulfur-based polymetal composite according to any one of claims 1 to 5, wherein said step 3 comprises: introducing carbon tetrafluoride gas, and depositing a uniform carbon and fluorine mixed layer on the surface of the precursor by chemical vapor deposition;
preferably, argon with the volume fraction of 20 percent is added into the carbon tetrafluoride gas as a protective gas;
preferably, the temperature of the chemical vapor deposition is 600-650 ℃;
preferably, the pressure of the chemical vapor deposition is 80-100 Pa;
preferably, the deposition speed of the chemical vapor deposition is 10-15 nm/min;
preferably, the deposition time of the chemical vapor deposition is 10-20 min.
7. The method for preparing a sulfur-based polymetal composite according to any one of claims 1 to 5, wherein said step 4 comprises: mixing the product obtained in the step (3) with a boron source, and then sintering at high temperature in a protective atmosphere to obtain a product with the surface coated with boron oxide;
preferably, the boron source comprises at least one of boric acid or boron oxide;
preferably, the mass ratio of the boron source to the product in the step 3 is 1 (50-500);
preferably, the product obtained in the step 3 and a boron source are mixed in a mixing tank, the rotating speed during mixing is 150-250 r/min, and the mixing time is 60-90 min;
preferably, the protective atmosphere comprises any one of argon or nitrogen or a combination of both;
preferably, the sintering temperature is 250-350 ℃, and the sintering time is 5-7 h.
8. The sulfur-based polymetal composite material produced by the production method according to any one of claims 1 to 7.
9. A lithium ion battery pole piece comprising the sulfur-based multi-metal composite of claim 8.
10. A lithium ion battery comprising the lithium ion battery pole piece of claim 9.
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