CN114899386A - Preparation method and application of MXene/metal compound composite material - Google Patents
Preparation method and application of MXene/metal compound composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002841 Lewis acid Substances 0.000 claims abstract description 29
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000002905 metal composite material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005530 etching Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000339 iron disulfide Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/58—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
- H01M4/62—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation method and application of an MXene/metal compound composite material, wherein a metal compound grows in situ in an MXene matrix. The preparation method comprises the following steps: 1) mixing a precursor MAX phase material, Lewis acid molten salt and inorganic salt, and reacting at a high temperature to prepare the MXene/metal composite material in one step; 2) carrying out reactions such as sulfuration/phosphorization/selenization/tellurization on the material obtained in the step 1) to prepare the MXene/metal compound composite material. The preparation method has the characteristics of simplicity, short experimental steps, strong universality, small damage to MXene, high experimental safety and the like, and when the prepared MXene/metal compound composite material is used as the negative electrode of the alkali metal ion rechargeable battery, the MXene/metal compound composite material has good structural stability, so that the MXene/metal compound composite material has excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nano materials, and particularly relates to a preparation method and application of an MXene/metal compound composite material.
Background
Due to the increasing severity of energy and environmental issues, secondary alkali metal ion batteries including lithium ion batteries, sodium ion batteries and potassium ion batteries have received a great deal of attention in recent years, and despite the fact that their development has made great progress, the development of high-performance negative electrode materials has still had some difficulty. The metal compound is considered as a potential negative electrode material due to its high theoretical specific capacity, but it exhibits poor cycle performance and rate performance due to its large volume stress and poor ionic and electronic conductivity during charge and discharge.
As an emerging member of the two-dimensional materials field, the transition metal carbides, nitrides or carbonitrides known as MXenes have excellent redox activity, large and controllable interlayer spacing, electronic conductivity at the metal level, low alkali ion migration barrier and excellent stress release capability. Therefore, researchers in recent years improve the electrochemical performance of the metal compound cathode by preparing the MXene/metal compound composite material, however, the preparation process of the MXene/metal compound composite material is complex at present, the steps of firstly preparing the MXene, then adsorbing different metal ions and finally performing post-treatment are basically followed, hydrofluoric acid is inevitably used in the conventional preparation process directly or indirectly, the experimental safety is reduced, and in addition, the conventional preparation process needs to be performed in water, so that the MXene is oxidized or degraded.
Recently, a lewis acid molten salt etching strategy is proposed for preparing MXene, the method has the advantages of high safety, controllable MXene surface groups and the like, in addition, metals are generated in situ in an MXene matrix in the process of etching MAX phase precursors by using lewis acid molten salt, however, the current research is to remove the metals generated in the etching process so as to obtain pure MXene with various end group modifications, and therefore, the reasonable utilization of the metals generated in situ in the process of preparing MXene by using lewis acid molten salt etching MAX is worthy of further exploration.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of an MXene/metal compound composite material.
The technical scheme adopted by the invention is as follows:
a preparation method of an MXene/metal compound composite material comprises the following steps:
(1) grinding and mixing the MAX phase material of the precursor, Lewis acid molten salt and inorganic salt, removing unreacted Lewis acid molten salt and inorganic salt after the reaction is finished in a tube furnace at high temperature, and drying to obtain the MXene/metal composite material.
(2) Heating the MXene/metal composite material prepared in the step (1) and a reagent required by vulcanization, phosphorization, selenization or tellurization in a tubular furnace, and reacting to prepare the MXene/metal compound composite material.
Preferably, the precursor MAX phase material is Ti 3 AlC 2 、Ti 3 SiC 2 、Ti 3 AlCN、 Ta 3 AlC 2 、Ti 2 AlC、Ti 2 AlN、Ta 2 AlC、Ti 2 SnC、Ti 2 GaC、V 2 AlC、V 2 GaC、 Nb 2 AlC、Nb 2 SnC、Mo 2 AlC、Mo 2 GaN、Hf 2 AlC、Hf 2 AlN、Sc 2 AlC、Zr 2 AlC、 Zr 2 SnC、Ta 4 AlC 3 、Ti 4 AlN 3 、Nb 4 AlC 3 Any one or a combination of two or more of them.
Preferably, the Lewis acid molten salt is FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 、 SnCl 2 、CdCl 2 、FeBr 2 、CoBr 2 、NiBr 2 、CuBr 2 、ZnBr 2 、SnBr 2 、CdBr 2 、FeI 2 、 CoI 2 、NiI 2 、CuI 2 、ZnI 2 、CdI 2 Any one or more of them.
More preferably, the Lewis acid molten salt is FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、 ZnCl 2 、FeBr 2 、CoBr 2 、NiBr 2 、CuBr 2 、FeI 2 、CuI 2 Any one or more of them.
Preferably, the inorganic salt is any one or more of NaCl, NaF, NaI, LiCl, KCl, KI, NaBr and KBr.
Preferably, the metal compound is any one or more of metal sulfide, metal phosphide, metal selenide and metal telluride.
Preferably, the reagent required for sulfurizing, phosphorizing, selenizing or tellurizing the material obtained in step (1) is S, CH 4 N 2 S、NaH 2 PO 2 And powder materials of Se and Te.
Preferably, the high-temperature reaction in the step (1) needs to be carried out under an inert atmosphere, the temperature of the high-temperature reaction is 500-750 ℃, the reaction time is 10-24h, and the molar ratio of the MAX phase material, the Lewis acid molten salt and the inorganic salt is 1: (1-5): (4-8).
Preferably, the reaction in the step (2) needs to be carried out under an inert atmosphere, the reaction temperature is 300-450 ℃, the reaction time is 2-8h, and the molar ratio of the MXene/metal composite material to the reagents required for vulcanization, phosphorization, selenization or tellurization is 1: (5-100).
The MXene/metal compound composite material prepared by the method can be used as a negative electrode material of a lithium ion battery, a sodium ion battery or a potassium ion battery.
The reaction mechanism for preparing MXene by using Lewis acid molten salt to etch MAX precursor can be expressed as equations (1) - (2), wherein MAX precursor is Ti 3 AlC 2 The Lewis acid molten salt is FeCl 2 For example, the equation can show that Ti is present during the preparation process 3 C 2 In-situ growth of metallic Fe in MXene matrix, the existing research is to grow metallic Fe in situThe formed metal is removed so as to facilitate the research on the physical and chemical properties of MXene with different end groups, however, when the single MXene is used as the negative electrode material of the alkali metal ion rechargeable battery, the single MXene shows low specific discharge capacity, and in addition, the metals generated in situ, such as Fe, Co, Ni, Cu and the like, do not have electrochemical reaction activity per se, so that how to effectively utilize the metals generated in situ in the process of etching MAX by the Lewis acid molten salt to construct the high-performance negative electrode material is worthy of further exploration.
Ti 3 AlC 2 +1.5FeCl 2 →Ti 3 C 2 +AlCl 3 ↑+1.5Fe (1)
Ti 3 C 2 +FeCl 2 →Ti 3 C 2 Cl 2 +Fe (2)
Compared with the prior art, the preparation method directly carries out reactions such as sulfuration/phosphorization/selenization/tellurization and the like on the MXene/metal composite material obtained in the process of etching MAX phase precursor by the Lewis acid molten salt to prepare the MXene/metal compound composite material, and the metal compound has high theoretical specific capacity when being used as a secondary alkali metal ion battery cathode material. Compared with the general method of firstly preparing MXene and then adsorbing metal ions, in the MXene/metal composite material obtained by etching MAX by using Lewis acid molten salt, metal grows in situ in the MXene matrix, the combination of the MXene and the metal is stronger, which plays a crucial role in showing excellent electrochemical performance when the MXene/metal compound obtained by subsequent preparation is used as an electrode material, because if the combination of the MXene matrix and the metal compound is not strong, the metal compound is easy to fall off from the MXene matrix due to larger volume expansion in the long-cycle process, and further gradually decays specific capacity, therefore, compared with the MXene/metal compound anode material prepared by using the general method, the MXene/metal compound anode material prepared by using the method is based on Lewis acid, and the metal ion adsorption method is characterized in thatThe MXene/metal compound negative electrode material prepared by the silicic acid molten salt etching route has better structural stability in a long-cycle process, and further shows more excellent electrochemical performance. In addition, the composite material is prepared by adopting a two-step method instead of a one-step method, the reaction temperature for preparing the MXene/metal composite material in the first step is 500- 2 PO 2 They decompose to produce H in the range of 300-350 DEG C 2 S or PH 3 If the gas and the two steps are mixed together to carry out high-temperature reaction, the second step reaction is started when the first step reaction is not started, and finally the expected MXene/metal compound composite material cannot be obtained. In addition, the preparation method avoids using commonly used highly toxic reagents such as hydrofluoric acid and the like to prepare MXene, greatly improves the experimental safety, and finally reduces the oxidation and degradation of MXene in the preparation process because MXene is usually oxidized in water.
It can be seen that the invention has the following beneficial effects:
the preparation method has the characteristics of simplicity, short experimental steps, strong universality, small damage to MXene, high experimental safety and the like, and when the prepared MXene/metal compound composite material is used as the negative electrode of the alkali metal ion rechargeable battery, the MXene/metal compound composite material has good structural stability and shows excellent cycle performance.
Drawings
FIG. 1 shows Ti prepared in example 1 3 C 2 /FeS 2 XRD pattern of the composite.
FIG. 2 shows pure Ti prepared in example 1 3 C 2 XRD pattern of the material.
FIG. 3 shows Ti prepared in example 1 3 C 2 /FeS 2 SEM image of the composite material.
FIG. 4 shows pure Ti prepared in example 1 3 C 2 SEM image of material.
FIG. 5 shows Ti prepared in example 1 3 C 2 /FeS 2 Composite material and pure Ti 3 C 2 MXene is used as an electrochemical performance graph of a lithium ion battery cathode.
FIG. 6 shows Ti in example 2 3 C 2 /FeS 2 The electrochemical performance of the composite material as a negative electrode of a sodium-ion battery is shown.
FIG. 7 shows Ti prepared in example 3 2 C/CoS y XRD pattern of the composite.
FIG. 8 shows Ti prepared in example 3 2 C/CoS y SEM image of the composite material.
FIG. 9 shows Ti prepared in example 3 2 C/CoS y The electrochemical performance diagram of the composite material as the negative electrode of the lithium ion battery.
FIG. 10 shows Ti prepared in example 4 3 C 2 /NiS y XRD pattern of the composite.
FIG. 11 shows Ti prepared in example 4 3 C 2 /NiS y SEM image of the composite material.
FIG. 12 shows Ti prepared in example 4 3 C 2 /NiS y The electrochemical performance diagram of the composite material as the negative electrode of the lithium ion battery.
FIG. 13 shows Ti in example 5 3 C 2 /NiS y The electrochemical performance of the composite material as a negative electrode of a sodium-ion battery is shown.
FIG. 14 shows Nb prepared in example 6 2 XRD pattern of C/CuS composite.
FIG. 15 shows Nb prepared in example 6 2 SEM image of C/CuS composite material.
FIG. 16 shows Nb prepared in example 6 2 And the electrochemical performance diagram of the C/CuS composite material as the negative electrode of the potassium ion battery.
Detailed Description
In order to make the technical solution and advantages of the present method more clearly understood, the present invention is further described in detail below with reference to several embodiments and the accompanying drawings, and it should be noted that the specific embodiments described herein are only used for explaining the present invention and are not used for limiting the present invention.
Example 1
(1) Precursor Ti 3 AlC 2 MAX、FeCl 2 The Lewis acid molten salt and the inorganic salt (NaCl + KCl) are ground and mixed according to the molar ratio of 1:3:5 to obtain a mixture.
(2) Placing the mixture in an alumina porcelain boat, then placing the alumina porcelain boat in a tubular furnace to react for 20 hours at 700 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, taking out the porcelain boat, washing away the residual Lewis acid molten salt and inorganic salt by deionized water, and then drying in vacuum to obtain Ti 3 C 2 a/Fe composite material.
(3) Mixing Ti 3 C 2 Composite of/Fe and CH 4 N 2 S is respectively placed in two alumina porcelain boats according to the molar ratio of 1:10, wherein CH is filled in the two alumina porcelain boats 4 N 2 Placing the porcelain boat of S at the upstream of the tube furnace, then reacting for 3h at 300 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, and taking out the porcelain boat to obtain Ti 3 C 2 /FeS 2 And (3) obtaining a powder product.
(4) In addition, for comparison of electrochemical properties, Ti obtained by the reaction in the step (2) was subjected to 3 C 2 Washing MXene/Fe composite material with dilute hydrochloric acid to remove metal Fe to obtain pure Ti 3 C 2 MXene。
Ti prepared in steps (3) and (4) of this example was used 3 C 2 /FeS 2 And pure Ti 3 C 2 X-ray diffraction (XRD) analysis of MXene revealed that the diffraction peaks of the sample after 10 ℃ corresponded mainly to the crystal configuration of iron disulfide of pyrite and hematite, and that the peak at 7.82 ℃ was attributed to Ti, as shown in FIG. 1 3 C 2 MXene. FIG. 2 is pure Ti 3 C 2 The XRD pattern of MXene showed the peak with the highest intensity as the (002) peak before 10 ℃. FIG. 3 is a field emission Scanning Electron Microscope (SEM) for Ti 3 C 2 /FeS 2 FeS can be found from the image obtained by observing the appearance 2 The particles are uniformly grown on Ti 3 C 2 MXene on a substrate. FIG. 4 shows pure Ti 3 C 2 The SEM image of MXene can find that MXene presents a typical layered structure, and the surface is not loaded by metal Fe particles。
Ti produced in the example 3 C 2 /FeS 2 The application is as the negative electrode material of the lithium ion battery:
respectively weighing a certain amount of electrochemical active material, acetylene black conductive agent and sodium carboxymethylcellulose binder by a balance, wherein the mass ratio of the electrochemical active material to the acetylene black conductive agent to the sodium carboxymethylcellulose binder is 8:1:1, adding a proper amount of deionized water, stirring for 6 hours to form slurry, then coating the slurry on a copper foil by blade, drying for 12 hours in a vacuum drying oven at 70 ℃, and finally cutting into electrode plates with the diameter of 14 mm.
The electrode slice obtained above is selected as a negative electrode, a metal lithium slice is selected as a counter electrode, Celgard 2300 is a diaphragm, and 1M LiPF 6 And (DMC: EMC: FEC 1: 1: 1) is used as an electrolyte, a CR2032 button cell is assembled in a glove box filled with argon, finally, the cell is sealed by a sealing machine, and the cell is subjected to an electrochemical performance test by a Land test system after being kept still for 10 hours. FIG. 5 is pure Ti 3 C 2 MXene and Ti 3 C 2 /FeS 2 As the cycle performance chart of the lithium ion battery cathode material at 1A/g, Ti can be seen 3 C 2 /FeS 2 The specific capacity of the cathode material is about 615mAh/g after the cathode material is circulated for 300 circles, the cathode material has high discharge specific capacity and circulation stability, and pure Ti without metallic Fe simple substance 3 C 2 MXene, which shows low specific discharge capacity, proves that the electrochemical performance of MXene can be greatly improved by reasonably treating the metal generated in situ in the process of preparing MXene by a Lewis acid molten salt method.
Example 2
This example uses Ti as prepared in example 1 3 C 2 /FeS 2 The preparation method of the electrode plate is the same as that of the electrode plate in example 1, the metal sodium plate is used as a counter electrode, the glass fiber is used as a diaphragm, and 1M NaPF is used as a negative electrode material of the sodium-ion battery 6 (Diglyme) is used as electrolyte, a CR2032 button battery is assembled in a glove box filled with argon, finally, the battery is sealed by a sealing machine, and the battery is subjected to electrochemical performance test by a Land test system after standing for 10 hours. FIG. 6 is Ti 3 C 2 /FeS 2 As sodium ionThe cycle performance diagram of the cathode material of the sub-battery under the current density of 5A/g shows that the specific capacity is about 480mAh/g after 400 cycles of cycle, and the cathode material shows excellent electrochemical performance.
Example 3
(1) Precursor Ti 2 AlC MAX、CoCl 2 The Lewis acid molten salt and the inorganic salt (NaCl + KCl) are ground and mixed according to the molar ratio of 1:4:5 to obtain a mixture.
(2) Placing the mixture in an alumina porcelain boat, then placing the alumina porcelain boat in a tubular furnace to react for 24 hours at 750 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, taking out the porcelain boat, washing away the residual Lewis acid molten salt and inorganic salt by deionized water, and then drying in vacuum to obtain Ti 2 C/Co composite material.
(3) Mixing Ti 2 C/Co composite and CH 4 N 2 S is respectively placed in two alumina porcelain boats according to the molar ratio of 1:15, wherein CH is filled in the two alumina porcelain boats 4 N 2 Placing the porcelain boat of S at the upstream of the tube furnace, then reacting for 3h at 350 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, and taking out the porcelain boat to obtain Ti 2 C/CoS y (including Co) 3 S 4 And CoS 2 ) And (3) obtaining a powder product.
For Ti prepared in step (3) of this example 2 C/CoS y By performing X-ray diffraction analysis, as shown in FIG. 7, the diffraction peak of the sample after 10 ℃ mainly corresponded to Co of PDF No. 42-1448 3 S 4 And CoS with PDF numbers 41-1471 2 FIG. 8 is a schematic view of a field emission type scanning electron microscope for Ti 2 C/CoS y CoS can be found from the image obtained by observing the appearance y The particles are uniformly grown on Ti 2 C MXene on a substrate.
Ti produced in the example 2 C/CoS y The composite material is applied to the negative electrode of the lithium ion battery, the preparation process of the specific electrode plate and the assembly process of the battery are the same as those in the embodiment 1, and FIG. 9 shows Ti 2 C/CoS y As a cycle performance diagram of the lithium ion battery cathode material under the current density of 2000mA/g, the specific capacity is about 450mAh/g after 800 cycles of cycle, and the lithium ion battery cathode material has very high dischargeSpecific capacity, and excellent electrochemical performance.
Example 4
(1) Precursor Ti 3 SiC 2 MAX、NiBr 2 And (3) grinding and mixing the Lewis acid molten salt and the inorganic salt (NaI + KI) according to the molar ratio of 1:3:6 to obtain a mixture.
(2) Placing the mixture in an alumina porcelain boat, then placing the alumina porcelain boat in a tubular furnace to react for 15 hours at 650 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, taking out the porcelain boat, washing away the residual Lewis acid molten salt and inorganic salt by deionized water, and then drying in vacuum to obtain Ti 3 C 2 a/Ni composite material.
(3) Mixing Ti 3 C 2 Grinding and mixing the/Ni composite material and sulfur powder according to a molar ratio of 1:20, placing the mixture into an alumina porcelain boat, then placing the alumina porcelain boat into a tubular furnace to react for 2.5 hours at 320 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, and taking out the porcelain boat to obtain Ti 3 C 2 /NiS y (including NiS) 2 NiS and Ni 3 S 4 ) And (3) obtaining a powder product.
For Ti prepared in step (3) of this example 3 C 2 /NiS y By X-ray diffraction analysis, as shown in FIG. 10, the main diffraction peak of the sample corresponds to NiS with PDF No. 11-0099 2 NiS with PDF number of 02-1280 and Ni with PDF number of 43-1469 3 S 4 FIG. 11 shows a field emission scanning electron microscope for Ti 3 C 2 /NiS y NiS can be found from the image obtained by observing the appearance y The particles are uniformly grown on Ti 3 C 2 MXene on a substrate.
Ti produced in the example 3 C 2 /NiS y The preparation process of the specific electrode plate and the assembly process of the battery applied as the lithium ion battery cathode material are the same as those in example 1, and fig. 12 shows Ti 3 C 2 /NiS y As a cycle performance diagram of the lithium ion battery negative electrode material under the current density of 1500mA/g, the specific capacity is about 524mAh/g after 1000 cycles of cycle, and the lithium ion battery negative electrode material has high specific discharge capacity and excellent cycle performance.
Example 5
This example uses Ti as prepared in example 4 3 C 2 /NiS y As a negative electrode material of a sodium ion battery, wherein the preparation method of an electrode plate is the same as that of example 4, a metal sodium plate is used as a counter electrode, glass fiber is used as a diaphragm, and 1M NaPF is adopted in the process of assembling the battery 6 (Diglyme) is used as electrolyte, a CR2032 button battery is assembled in a glove box filled with argon, finally, the battery is sealed by a sealing machine, and the battery is subjected to electrochemical performance test by a Land test system after standing for 10 hours. FIG. 13 is Ti 3 C 2 /NiS y As a circulation performance diagram of the sodium ion battery cathode material under the current density of 2000mA/g, the specific capacity is about 340mAh/g after 800 cycles of circulation, and the sodium ion battery cathode material shows excellent electrochemical performance.
Example 6
(1) Precursor Nb 2 AlC MAX、CuI 2 The Lewis acid molten salt and the inorganic salt (NaBr + KBr) are ground and mixed according to the molar ratio of 1:3:7 to obtain a mixture.
(2) Placing the mixture in an alumina porcelain boat, then placing the alumina porcelain boat in a tubular furnace to react for 22 hours at the temperature of 600 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, taking out the porcelain boat, washing away the residual Lewis acid molten salt and inorganic salt by deionized water, and then drying in vacuum to obtain Nb 2 C/Cu composite material.
(3) Mixing Nb with 2 Grinding and mixing the C/Cu composite material and sulfur powder according to a molar ratio of 1:12, then placing the mixture in a tubular furnace to react for 2.5 hours at 370 ℃ under the protection of argon atmosphere, waiting for the temperature to be reduced to room temperature after the reaction is finished, taking out a porcelain boat, and obtaining Nb 2 C/CuS powder product.
For Nb prepared in step (3) of this example 2 X-ray diffraction analysis of C/CuS As shown in FIG. 14, the diffraction peak of the sample mainly corresponds to CuS with PDF number 06-0464, FIG. 15 is Nb using field emission scanning electron microscope 2 The image obtained by observing the appearance of the C/CuS shows that CuS particles uniformly grow in Nb 2 C MXene on a substrate.
Nb obtained in the example 2 The C/CuS is applied as a negative electrode material of a potassium ion battery,
respectively weighing a certain amount of Nb by using a balance 2 C/CuS, an acetylene black conductive agent and a polyvinylidene fluoride binder, wherein the mass ratio of the C/CuS to the acetylene black conductive agent to the polyvinylidene fluoride binder is 8:1:1, a proper amount of N-methyl pyrrolidone is added and stirred for 6 hours to form slurry, the slurry is coated on a copper foil in a scraping mode, the copper foil is dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃, and finally the copper foil is cut into electrode plates with the diameter of 14 mm.
Selecting the obtained electrode plate as negative electrode, metal potassium plate as counter electrode, glass fiber as diaphragm, and 0.8M KPF 6 And (EC: DEC ═ 1: 1) is used as an electrolyte, a CR2032 button cell is assembled in a glove box filled with argon, finally, the cell is sealed by a sealing machine, and the cell is subjected to an electrochemical performance test by a Land test system after standing for 10 hours. FIG. 16 is Nb 2 The C/CuS is used as a cycle performance diagram of the potassium ion battery cathode material under the current density of 1000mA/g, the specific capacity is about 256mAh/g after 500 cycles of cycle, and the excellent cycle stability is shown.
In conclusion, the preparation method of the MXene/metal compound composite material provided by the invention has the characteristics of short experimental steps, small damage to MXene, high experimental safety and the like, simultaneously realizes reasonable utilization of Lewis acid molten salt etching products, shows excellent electrochemical performance when being used as the cathode of a lithium ion battery, a sodium ion battery or a potassium ion battery, and has wide application prospect.
It should be noted that the above mentioned embodiments are only examples and are not intended to limit the scope of the present invention, and all equivalent flow changes made by using the contents of the present specification and the attached drawings, or other related fields, should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the MXene/metal compound composite material is characterized by comprising the following steps:
the method comprises the following steps: grinding and mixing a MAX phase material of the precursor, Lewis acid molten salt and inorganic salt, removing unreacted Lewis acid molten salt and inorganic salt after the reaction is finished in a tubular furnace at high temperature, and drying to obtain an MXene/metal composite material;
step two: and (3) heating the MXene/metal composite material prepared in the step one and a reagent required by vulcanization, phosphorization, selenization or tellurization in a tubular furnace to prepare the MXene/metal compound composite material.
2. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the precursor MAX phase material is Ti 3 AlC 2 、Ti 3 SiC 2 、Ti 3 AlCN、Ta 3 AlC 2 、Ti 2 AlC、Ti 2 AlN、Ta 2 AlC、Ti 2 SnC、Ti 2 GaC、V 2 AlC、V 2 GaC、Nb 2 AlC、Nb 2 SnC、Mo 2 AlC、Mo 2 GaN、Hf 2 AlC、Hf 2 AlN、Sc 2 AlC、Zr 2 AlC、Zr 2 SnC、Ta 4 AlC 3 、Ti 4 AlN 3 、Nb 4 AlC 3 Any one or a combination of two or more of them.
3. The method of claim 1, wherein the MXene/metal compound composite is prepared by the following steps: the Lewis acid molten salt is FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 、SnCl 2 、CdCl 2 、FeBr 2 、CoBr 2 、NiBr 2 、CuBr 2 、ZnBr 2 、SnBr 2 、CdBr 2 、FeI 2 、CoI 2 、NiI 2 、CuI 2 、CdI 2 Any one or more of them.
4. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the inorganic salt is any one or more of NaCl, NaF, NaI, LiCl, KCl, KI, NaBr and KBr.
5. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the metal compound is any one or more of metal sulfide, metal phosphide, metal selenide and metal telluride.
6. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the reagent required by the sulfuration, the phosphorization, the selenization or the tellurization is S, CH 4 N 2 S、NaH 2 PO 2 And one or more of powder materials of Se and Te.
7. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the high-temperature reaction in the first step needs to be carried out in an inert atmosphere, the temperature of the high-temperature reaction is 500-750 ℃, the reaction time is 10-24h, and the molar ratio of the MAX phase material, the Lewis acid molten salt and the inorganic salt is 1: (1-5): (4-8).
8. The method for preparing MXene/metal compound composite material according to claim 1, wherein: the reaction in the second step needs to be carried out in an inert atmosphere, the reaction temperature is 300-450 ℃, the reaction time is 2-8h, and the molar ratio of the MXene/metal composite material to the reagents required by vulcanization, phosphorization, selenization or tellurization is 1: (5-100).
9. Use of an MXene/metal compound composite prepared according to the process of any one of claims 1-8, wherein: the prepared MXene/metal compound composite material is used as a negative electrode material of a lithium ion battery, a sodium ion battery or a potassium ion battery.
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