CN116387481A - Preparation method and application of heterostructure yolk shell type double transition metal selenide composite material - Google Patents
Preparation method and application of heterostructure yolk shell type double transition metal selenide composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 45
- 210000002969 egg yolk Anatomy 0.000 title claims abstract description 40
- -1 transition metal selenide Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 34
- 230000007704 transition Effects 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
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- 239000006230 acetylene black Substances 0.000 claims description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- 235000011087 fumaric acid Nutrition 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 10
- 102000020897 Formins Human genes 0.000 description 8
- 108091022623 Formins Proteins 0.000 description 8
- 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 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
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- 239000013082 iron-based metal-organic framework Substances 0.000 description 6
- 239000002091 nanocage Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910020598 Co Fe Inorganic materials 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002519 Co-Fe Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000012546 transfer Methods 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—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
- H01M4/58—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
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a preparation method and application of a heterostructure yolk shell type double transition metal selenide composite material. The chemical formula of the composite material is TM 1 Se 2 @TM 1 Se 2 /TM 2 Se 2 Wherein, TM 1 And TM 2 Respectively representing two different transition metal elements. The composite material prepared by the invention has uniform particles, a yolk shell structure has large specific surface area, a thin shell and an internal gap enable electrolyte to fully permeate, buffer space can be provided for volume expansion, the structure is kept stable, and the composite material is prepared from TM 1 Se 2 And TM 2 Se 2 The bimetal synergistic effect generated by the heterostructure promotes sodium ion diffusion and improves the multiplying power performance of the battery. In addition, the invention relates to a simple preparation methodThe single-component composite material has wide application range, and the prepared composite material has excellent multiplying power performance and cycle performance.
Description
Technical Field
The invention relates to the technical field of electrochemical energy materials, in particular to a preparation method of a heterostructure yolk shell type double transition metal selenide composite material and application of the heterostructure yolk shell type double transition metal selenide composite material in a sodium ion battery anode material.
Background
With the increasing global demand for efficient and clean energy, the application prospect of new energy sources such as wind energy, solar energy, tidal energy and the like is wider. While power grid systems are rapidly spreading and portable new energy sources are moving into the day to day, energy storage devices are attracting attention as the most critical one of them. Over the last several decades, lithium ion batteries have been widely studied and used, and the advantages of electrochemical energy storage technology have been gradually revealed. However, the large-scale popularization of the lithium ion battery is limited by the problem of limited lithium ion resources, so that the cost of the battery is high. Sodium and lithium belong to the same main group of elements, have similar chemical properties, high abundance, environmental friendliness and wide application prospect. However, since the radius of sodium ions is larger, when the graphite anode of the lithium ion battery is used for anode materials of the sodium ion battery, the graphite anode cannot be reversibly inserted into or extracted from an effective potential window, and the existing common carbon-based anode materials, titanium-based anode materials and the like have the problems of difficult insertion of sodium ions, poor conductivity and the like.
In recent years, the transition metal selenide has the advantages of higher theoretical specific capacity, more stable structure, narrower energy band gap and the like, and the chemical bond of transition metal-selenium is weaker than that in sulfide and oxide, so that rapid intercalation/deintercalation of sodium ions in the structure is facilitated, and the material can be widely applied to negative electrode materials of sodium ion batteries. However, the transition metal selenide has poor electron conductivity and tends to cause a large volume change during intercalation/deintercalation of sodium ions. The poor electronic conductivity results in that the actual specific capacity of the transition metal selenide in the application process is much lower than the theoretical specific capacity, which is not beneficial to the industrialized production of high-capacity batteries; large volume changes tend to reduce the cycling stability of the battery and may even present safety concerns if applied in large scale energy storage technologies. The invention of CN201910976902.1 uses a cobalt/iron bi-metal heterostructure to improve electron conduction, but the carbon coating means to improve stability does not significantly inhibit volume expansion, and the carbon layer of the non-sodium ion storage unit tends to cause a decrease in specific capacity.
Disclosure of Invention
The invention provides a preparation method and application of a hetero-structure yolk shell type double-transition metal sodium selenide battery anode material, which has the advantages of good electron conduction, high sodium storage capacity, small volume change, large specific surface area, uniform particles and excellent multiplying power and cycle performance. The heterostructure yolk shell type double transition metal selenide sodium ion battery cathode material provided by the invention promotes electron conduction through the synergistic effect of double transition metals, and meanwhile, the unique yolk shell structure of the material enables the material to reduce volume change, obtain larger specific surface area, increase the contact area of the electrode material and electrolyte and promote reaction kinetics.
A preparation method of a heterostructure yolk shell type double transition metal selenide composite material comprises the following steps:
s1, organic ligand reagent and TM 1 Dissolving the source in a reagent, and sequentially carrying out hydrothermal reaction, cooling, centrifugation, washing and drying on the solution to obtain a transition metal-organic framework; wherein the TM 1 The source is one or more of nitrate, phosphate, sulfate and chloride of Ti, cr, mn, fe, co, ni, cu or Zn;
s2, uniformly dispersing the transition metal-organic framework prepared in the step S1 in a reagent to obtain a solution A; TM is put into 2 Dissolving a source and a precipitant in a reagent to obtain a solution B; mixing the solution A and the solution B, and sequentially carrying out heat preservation, cooling, centrifugation, washing and drying to obtain a transition metal-organic framework material coated by double transition metal hydroxide with a yolk shell structure; the TM 2 The source is one or more of nitrate, phosphate, sulfate and chloride of Ti, cr, mn, fe, co, ni, cu or Zn;
s3, under the protection of inert gas, annealing and heat treating the transition metal-organic frame material coated by the double transition metal hydroxide prepared in S2 and selenium powder with a certain proportion, and cooling along with a furnace to obtain a composite material TM 1 Se 2 @TM 1 Se 2 /TM 2 Se 2 。
Further, the TM described in S1 1 The ratio of the source to the organic ligand reagent is 1-5:5, the hydrothermal reaction temperature is 100-160 ℃, the time is 1-5 h, the drying temperature is 60-100 ℃, and the time is 8-24 h.
Further, in S2, the precipitant, the transition metal-organic framework, the TM 2 The mass ratio of the sources is 1-5:0.24:1, the temperature condition of heat preservation treatment is 60-90 ℃, the time condition is 4-12 h, the temperature condition of drying is 60-100 ℃, and the time condition is 8-24 h.
Further, in S3, the mass ratio of the transition metal-organic framework material coated by the double transition metal hydroxide to the selenium powder is 1:1-4;
placing a porcelain boat containing the transition metal-organic framework material coated by the double transition metal hydroxide and the selenium powder into a tube furnace, firstly heating to 200-400 ℃ under the mixed atmosphere of hydrogen/argon or hydrogen/nitrogen, and preserving heat for 1-6 h; then heating to 400-800 ℃ under nitrogen or argon atmosphere, preserving heat for 1-6 h, and heating at a speed of 2-8 ℃/min in two sections.
Further, the organic ligand reagent is one or more of fumaric acid, benzoic acid, oxalic acid and pyrazine;
the reagents in S1 and S2 are one or more of deionized water, methanol, ethanol, N-dimethylformamide, N-diethylformamide, acetonitrile and acetone;
the precipitant comprises one or more of ammonium chloride, urea, sodium hydroxide and sodium carbonate.
The heterostructure yolk shell type double transition metal selenide composite material prepared by the preparation method is prepared.
Further, the composite material has a hollow yolk-eggshell structure with a particle size of 1-2 microns.
The heterostructure yolk shell type double transition metal selenide composite material obtained by the preparation method is applied to preparation of the sodium ion battery anode active material.
The sodium ion battery comprises an electrode plate, a counter electrode, a diaphragm and electrolyte, wherein the electrode plate is prepared by mixing the heterostructure yolk shell type double transition metal selenide composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 5-7:1-2:1, the counter electrode is a sodium metal plate, the diaphragm is a glass fiber diaphragm, and the electrolyte is prepared by 1 mol.L -1 Sodium hexafluorophosphate is dissolved in diethylene glycol methyl ether.
The sodium ion battery comprises an electrode plate, a counter electrode, a diaphragm and electrolyte, wherein the electrode plate is prepared by mixing the heterostructure yolk shell type double transition metal selenide composite material, acetylene black and polyvinylidene fluoride in a mass ratio of 5-7:1-2:1, the counter electrode is made of a sodium vanadium phosphate positive electrode material, the diaphragm is made of a glass fiber diaphragm, and the electrolyte is prepared by mixing 1 mol.L of the heterostructure yolk shell type double transition metal selenide composite material with the acetylene black and the polyvinylidene fluoride in a mass ratio of 5-7:1-2:1 -1 Sodium hexafluorophosphate is dissolved in diethylene glycol methyl ether.
Compared with the prior art, the invention has the following beneficial effects:
(1) The heterostructure yolk shell type double transition metal selenide composite material prepared by the invention is a micron hollow yolk-eggshell structure particle, and the size of the heterostructure yolk shell type double transition metal selenide composite material is about 1-2 mu m. The closely connected bimetallic heterojunction is introduced, and the synergistic effect and multi-electron reaction of the bimetallic heterojunction provide favorable conditions for reducing the obstruction of electron conduction and improving the sodium capacity; the innovatively designed hollow yolk shell structure not only increases the contact area between the electrode material and the electrolyte, but also can reduce the volume change in the sodium insertion/removal process on the premise of not losing the tap density and the volume specific capacity of the electrode material, increases the specific surface area, improves the safety while improving the rate performance, and also improves the cycle performance of the cathode material.
(2) The composite material is used as a negative electrode material of a sodium ion battery, and the charge and discharge tests are carried out under different current density values in a certain voltage interval. Due to the synergistic effect of the double transition metals, electron transfer and sodium ion diffusion kinetics are promoted, and the egg shell layer of the double transition metal heterostructure has stable structure and no capacity loss, so that the material has excellent multiplying power and cycle performance, and is a reliable anode material for realizing high-capacity, high-power and long-service-life sodium ion batteries.
(3) The invention adopts the egg yolk shell structure which introduces the bimetal synergistic effect to promote electron transfer and designs the bimetal selenide to provide buffer space for volume change. The introduction of the bimetal synergistic effect is to use selenide of two transition metal elements, reduce the obstruction of charge transfer through rich multi-electron reaction and a unique built-in electric field, and promote electron transfer; the bimetallic selenide yolk shell structure has a certain hollow area reserved between the core and the shell, so that the damage of volume change to the circulation performance can be relieved, the shell layer also contains sodium ion storage sites without losing the capacity, in addition, the electrolyte fully contacts the cathode material due to the large specific surface area, and the multiplying power performance is improved.
(4) The preparation method provided by the invention has mild preparation conditions, firstly, a hydrothermal method is adopted to synthesize a transition metal-organic framework material, then another transition metal source is introduced, the transition metal source reacts at a certain temperature to form a double transition metal hydroxide coated transition metal-organic framework material with a yolk shell structure, and finally, the material is placed in a tubular furnace for selenizing to obtain a target material.
Drawings
FIGS. 1a-d are SEM images of heterostructure yolk shell type cobalt diselenide/iron diselenide material prepared in example 1 of the present invention.
Fig. 2a-b are TEM images of heterostructure yolk shell type cobalt diselenide/iron diselenide material prepared in example 1 of the present invention.
Fig. 3 is a graph showing the rate performance of a battery assembled from heterostructure yolk-shell cobalt diselenide/iron diselenide materials prepared in example 1 of the present invention.
FIG. 4 shows the low current density 0.2Ag for each of the cells assembled from the materials prepared in example 1 and comparative example 1 according to the present invention -1 The following cycle performance graph.
FIG. 5 shows a high current density 2Ag for a battery assembled from heterostructure yolk-shell cobalt diselenide/iron diselenide material prepared in example 1 of the present invention -1 The following cycle performance graph.
Detailed Description
The technical solutions adopted in the present invention will be clearly and specifically described below by way of examples and comparative examples, which are merely illustrative of the present invention and do not represent all the examples, without limiting the scope of the present invention. Various modifications and alterations of the present invention will be apparent to those skilled in the art based on this disclosure, and such equivalents are intended to fall within the scope of the present invention. The equipment and reagents used in the present invention are conventional commercially available products in the art, unless specifically stated otherwise.
Example 1 ]
S1, 0.233g fumaric acid and 0.325g FeCl 3 ·6H 2 O is dissolved in 20mL of N, N-dimethylformamide and stirred vigorously to form a transparent yellow solution, then the solution is transferred into a 50mL polytetrafluoroethylene lining stainless steel autoclave, the solution is heated for 2h at 120 ℃, the sample is collected centrifugally after cooling, the sample is washed with water and ethanol alternately for 3 times, and the solution is dried for 12h at 60 ℃ to obtain the iron-based metal-organic framework.
S2, performing ultrasonic dispersion on 60mg of the iron-based metal-organic framework in 20mL of ethanol for 5min to form a solution A, and then performing ultrasonic dispersion on 250mg of Co (NO) 3 ) 2 ·6H 2 O and 750mg of urea are dissolved in 30mL of distilled water to form a solution B, the A, B solution is poured into a 100mL glass bottle with a cover after being mixed, then the glass bottle is placed into an oven, the glass bottle is heated for 5 hours at 90 ℃ under the condition of no stirring, after cooling, the brown product is centrifugally collected, washed with water and ethanol for multiple times until no impurity exists, and dried for 12 hours at 60 ℃ to obtain the Co-Fe LDH yolk shell nanocage.
S3, placing the Co-Fe LDH yolk shell nano cage and selenium powder in the same porcelain boat according to the mass ratio of 1:2, placing the selenium powder at the upstream end of a tube furnace gas circuit, and then firstly placing the selenium powder in a hydrogen/argon mixed atmosphere at 2 ℃ for min -1 Is kept at 350 ℃ for 4 hours and then is kept at 2 ℃ for min under nitrogen atmosphere -1 The temperature rising rate of (2) is kept at 400 ℃ for 1.5h, and finally the mixture is cooled along with a furnace to obtain the composite material FeSe 2 @CoSe 2 /FeSe 2 Heterostructure yolk shell polyhedrons.
Example 2 ]
S1, 0.245g of benzoic acid and 0.581g of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 20mL of absolute ethyl alcohol and is vigorously stirred to form a transparent green solution, then the solution is transferred into a 50mL polytetrafluoroethylene lining stainless steel autoclave, the solution is heated for 5h at 110 ℃, the sample is centrifugally collected after cooling, the sample is alternately washed for 3 times by water and ethanol, and the solution is dried for 24h at 80 ℃ to obtain the nickel-based metal-organic framework.
S2, performing ultrasonic dispersion on 60mg of the nickel-based metal-organic framework in 20mL of methanol for 5min to form a solution A. 250mg Co (NO) 3 ) 2 ·6H 2 O and 1250mg of sodium carbonate are dissolved in 30mL of distilled water to form a solution B, A, B solution is mixed and poured into a 100mL glass bottle with a cover, then the glass bottle is placed into an oven, the glass bottle is heated for 5h at 90 ℃ under the condition of no stirring, after cooling, the product is centrifugally collected, washed with water and ethanol for multiple times until no impurity exists, and dried for 24h at 60 ℃ to obtain the Co-Ni LDH yolk shell nanocage.
S3, placing the Co-Ni LDH yolk shell nano cage and selenium powder in the same porcelain boat according to the mass ratio of 1:4, wherein the selenium powder is placed at the upstream end of a tube furnace gas circuit. Then, the mixture is firstly treated under the mixed atmosphere of hydrogen and argon for 5 ℃ for min -1 Is kept at 300 ℃ for 4 hours and then is kept at 5 ℃ for min under argon atmosphere -1 The temperature is kept for 5 hours at 500 ℃, and finally the mixture is cooled along with the furnace to obtain the composite material NiSe 2 @CoSe 2 /NiSe 2 Heterostructure yolk shell polyhedrons.
Example 3 ]
S1, 0.180g oxalic acid and 0.108g FeCl 3 ·6H 2 O is dissolved in 20mL of deionized water and is vigorously stirred to form a transparent yellow solution, then the solution is transferred into a 50mL polytetrafluoroethylene lining stainless steel autoclave, the solution is heated for 3 hours at 120 ℃, the sample is centrifugally collected after cooling, and is alternately washed for 3 times with water and ethanol and dried for 8 hours at 60 ℃ to obtain the iron-based metal-organic framework.
S2, performing ultrasonic dispersion on 60mg of the iron-based metal-organic framework in 20mL of ethanol for 5min to form a solution A, and then performing ultrasonic dispersion on 250mg of C 4 H 14 MnO 8 And 250mg of urea are dissolved in 30mL of distilled water to form solution B, and A, B solution is mixedPour into a 100mL capped glass bottle. And then placing the glass bottle into an oven, heating for 12 hours at 60 ℃ without stirring, cooling, centrifugally collecting a product, washing with water and ethanol for multiple times until no impurity exists, and drying for 8 hours at 60 ℃ to obtain the Fe-Mn LDH yolk shell nanocage.
S3, placing the Fe-Mn LDH yolk shell nano cage and selenium powder in the same porcelain boat according to the mass ratio of 1:1, placing the selenium powder at the upstream end of a tube furnace gas circuit, and then firstly placing the selenium powder in a hydrogen/nitrogen mixed atmosphere at the temperature of 3 ℃ for min -1 Is kept at 350 ℃ for 6 hours and then is kept at 3 ℃ for min under nitrogen atmosphere -1 The temperature rising rate is kept at 500 ℃ for 6 hours, and finally the composite material FeSe is obtained after cooling along with the furnace 2 @MnSe 2 /FeSe 2 Heterostructure yolk shell polyhedrons.
The double transition metals selected in examples 1, 2 and 3 are iron/cobalt, nickel/cobalt and iron/manganese, respectively, and the organic ligand reagents selected are fumaric acid, benzoic acid and oxalic acid, respectively.
Example 4 ]
S1, respectively weighing 0.14g, 0.04g and 0.02g of the composite material, acetylene black and polyvinylidene fluoride prepared by the method described in the example 1 according to the mass ratio of 7:2:1, dissolving the materials in 1mL of NMP, and uniformly mixing the materials in a mixer to obtain the electrode slurry.
S2, uniformly coating the mixed electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 12 hours, cutting the aluminum foil into electrode wafers with the loading capacity of about 1mg, and assembling the electrode wafers by adopting a CR2032 type button cell.
S3, taking a negative plate made of a composite material as a working electrode, taking a metal sodium plate as a counter electrode, and adopting a glass fiber diaphragm and 1 mol.L -1 Sodium hexafluorophosphate (NaPF) 6 ) The electrolyte was dissolved in diethylene glycol methyl ether (DME) to assemble a battery and performance test was performed.
Example 5 ]
S1, respectively weighing 0.10g, 0.02g and 0.02g of the composite material prepared by the method in example 1, acetylene black and polyvinylidene fluoride according to the mass ratio of 5:1:1, dissolving the materials in 1mL of NMP, and uniformly mixing the materials in a mixer to obtain the electrode slurry.
S2, uniformly coating the mixed electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 12 hours, cutting the aluminum foil into electrode wafers with the loading capacity of about 1mg, and assembling the electrode wafers by adopting a CR2032 type button cell.
S3, taking a negative plate made of a composite material as a working electrode, taking a metal sodium plate as a counter electrode, and adopting a glass fiber diaphragm and 1 mol.L -1 Sodium hexafluorophosphate (NaPF) 6 ) The electrolyte was dissolved in diethylene glycol methyl ether (DME) to assemble a battery and performance test was performed.
Example 6 ]
S1, respectively weighing 0.10g, 0.02g and 0.02g of the composite material prepared by the method in example 1, acetylene black and polyvinylidene fluoride according to the mass ratio of 5:1:1, dissolving the materials in 1mL of NMP, and uniformly mixing the materials in a mixer to obtain the electrode slurry.
S2, uniformly coating the mixed electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 12 hours, cutting the aluminum foil into electrode wafers with the loading capacity of about 1mg, and assembling the electrode wafers by adopting a CR2032 type button cell.
S3, taking a negative plate made of a composite material as a working electrode, taking a sodium vanadium phosphate material as a counter electrode, and adopting a glass fiber diaphragm and 1 mol.L -1 Sodium hexafluorophosphate (NaPF) 6 ) The electrolyte was dissolved in diethylene glycol methyl ether (DME) to assemble a battery and performance test was performed.
Example 7 ]
S1, respectively weighing 0.14g, 0.04g and 0.02g of the composite material, acetylene black and polyvinylidene fluoride prepared by the method described in the example 1 according to the mass ratio of 7:2:1, dissolving the materials in 1mL of NMP, and uniformly mixing the materials in a mixer to obtain the electrode slurry.
S2, uniformly coating the mixed electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 12 hours, cutting the aluminum foil into electrode wafers with the loading capacity of about 1mg, and assembling the electrode wafers by adopting a CR2032 type button cell.
S3, taking a negative plate made of a composite material as a working electrode, taking a sodium vanadium phosphate material as a counter electrode, and adopting a glass fiber diaphragm and 1 mol.L -1 Sodium hexafluorophosphate (NaPF) 6 ) The electrolyte was dissolved in diethylene glycol methyl ether (DME) to assemble a battery and performance test was performed.
Comparative example 1 ]
S1, 0.233g fumaric acid and 0.325g FeCl 3 ·6H 2 O is dissolved in 20mL of N, N-dimethylformamide, and is vigorously stirred to form a transparent yellow solution, then the solution is transferred into a 50mL Teflon-lined stainless steel autoclave, the solution is heated for 2 hours at 120 ℃, and after cooling, the sample is centrifugally collected, is alternately washed with water and ethanol for 3 times, and is dried for 12 hours at 60 ℃ to obtain the iron-based metal-organic framework.
S2, performing ultrasonic dispersion on 60mg of the iron-based metal-organic framework in 20mL of ethanol for 5min to form a solution A, dissolving 750mg of urea in 30mL of distilled water to form a solution B, mixing A, B solutions, pouring the mixture into a 100mL glass bottle with a cover, placing the glass bottle into an oven, heating at 90 ℃ for 5h without stirring, cooling, centrifugally collecting a brown product, washing with water and ethanol for multiple times, and drying at 60 ℃ for 12h to obtain ferric hydroxide.
S3, placing ferric hydroxide and selenium powder in the same porcelain boat according to the mass ratio of 1:2, wherein the selenium powder is placed near the upstream end of the tube furnace. Then the mixture is firstly treated under the mixed atmosphere of hydrogen and argon for 2 ℃ for min -1 Is kept at 350 ℃ for 4 hours and then is kept at 2 ℃ for min under nitrogen atmosphere -1 The temperature is kept at 400 ℃ for 1.5h. Finally cooling along with the furnace to obtain the target material FeSe 2 。
Comparative example 2 ]
S1, respectively weighing 0.14g, 0.04g and 0.02g of the composite material, acetylene black and polyvinylidene fluoride prepared by the method described in the comparative example 1 according to the mass ratio of 7:2:1, dissolving the materials in 1mL of NMP, and uniformly mixing the materials in a mixer to obtain the electrode slurry.
S2, uniformly coating the mixed electrode slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven at the temperature of 100 ℃ for 12 hours, cutting the aluminum foil into electrode wafers with the loading capacity of about 1mg, and assembling the electrode wafers by adopting a CR2032 type button cell.
S3, taking a negative plate made of a composite material as a working electrode, taking a metal sodium plate as a counter electrode, and adopting glassFiber separator and 1 mol.L -1 Sodium hexafluorophosphate (NaPF) 6 ) The electrolyte was dissolved in diethylene glycol methyl ether (DME) to assemble a battery and performance test was performed.
FeSe as a composite material obtained in example 1 2 @CoSe 2 /FeSe 2 For example, the particle size is about 1-2 μm, and the Scanning Electron Microscope (SEM) and the Transmission Electron Microscope (TEM) are shown in FIGS. 1 and 2, respectively.
As shown in FIG. 3, the battery assembled in example 4 has a rate performance diagram with a voltage range of 0.3 to 2.9V and 0.1Ag -1 ，0.2Ag -1 ，0.5Ag -1 ，1Ag -1 ，2Ag -1 ，3Ag -1 5Ag -1 Constant current charge and discharge tests were carried out at current densities with specific discharge capacities of 708.8, 550.4, 539.2, 533.6, 522.8, 512.5 and 495.4mAh g, respectively -1 Exhibits excellent rate performance.
As shown in FIG. 4, the assembled batteries prepared in example 4 and comparative example 2 were prepared at low current densities of 0.2Ag, respectively -1 As can be seen from FIG. 4, the heterostructure yolk-shell type composite FeSe prepared in example 1 has the following cycle performance diagram 2 @CoSe 2 /FeSe 2 As the battery cathode material, the capacity and the stability of the battery are higher.
The assembled battery of example 4 is shown in FIG. 5 at 2Ag -1 As can be seen from FIG. 5, the material still has 529mAh g after 1800 times of charge and discharge -1 The specific capacity of the lithium ion battery is as high as 78%, the lithium ion battery has excellent cycle performance and long service life, and the lithium ion battery is an ideal negative electrode material for realizing high-capacity and high-power sodium ion batteries.
In this document, terms such as front, rear, upper, lower, etc. are defined by the positions of the components in the drawings and the positions of the components relative to each other, for the sake of clarity and convenience in expressing the technical solution. It should be understood that the use of such orientation terms should not limit the scope of the protection sought herein.
The embodiments described above and features of the embodiments herein may be combined with each other without conflict.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the heterostructure yolk shell type double transition metal selenide composite material is characterized by comprising the following steps of:
s1, organic ligand reagent and TM 1 Dissolving the source in a reagent, and sequentially carrying out hydrothermal reaction, cooling, centrifugation, washing and drying on the solution to obtain a transition metal-organic framework; wherein the TM 1 The source is one or more of nitrate, phosphate, sulfate and chloride of Ti, cr, mn, fe, co, ni, cu or Zn;
s2, uniformly dispersing the transition metal-organic framework prepared in the step S1 in a reagent to obtain a solution A; TM is put into 2 Dissolving a source and a precipitant in a reagent to obtain a solution B; mixing the solution A and the solution B, and sequentially carrying out heat preservation, cooling, centrifugation, washing and drying to obtain a transition metal-organic framework material coated by double transition metal hydroxide with a yolk shell structure; the TM 2 The source is one or more of nitrate, phosphate, sulfate and chloride of Ti, cr, mn, fe, co, ni, cu or Zn;
s3, under the protection of inert gas, annealing and heat treating the transition metal-organic frame material coated by the double transition metal hydroxide prepared in S2 and selenium powder with a certain proportion, and cooling along with a furnace to obtain a composite material TM 1 Se 2 @TM 1 Se 2 /TM 2 Se 2 。
2. The method for preparing a heterostructure yolk shell type double transition metal selenide composite according to claim 1, wherein the TM in S1 is 1 The ratio of the source to the organic ligand reagent is 1-5:5, the temperature of the hydrothermal reaction is 100-160 ℃, the time is 1-5 h, and the drying temperature condition is thatThe temperature is 60-100 ℃ and the time condition is 8-24 h.
3. The method for preparing a heterostructure yolk-shell double transition metal selenide composite according to claim 1, wherein the precipitant, the transition metal-organic framework, and the TM in S2 2 The mass ratio of the sources is 1-5:0.24:1, the temperature condition of heat preservation treatment is 60-90 ℃, the time condition is 4-12 h, the temperature condition of drying is 60-100 ℃, and the time condition is 8-24 h.
4. The method for preparing a heterostructure yolk shell type double transition metal selenide composite material according to claim 1, wherein in S3, a mass ratio of the double transition metal hydroxide coated transition metal-organic frame material to the selenium powder is 1:1-4;
placing a porcelain boat containing the transition metal-organic framework material coated by the double transition metal hydroxide and the selenium powder into a tube furnace, firstly heating to 200-400 ℃ under the mixed atmosphere of hydrogen/argon or hydrogen/nitrogen, and preserving heat for 1-6 h; then heating to 400-800 ℃ under nitrogen or argon atmosphere, preserving heat for 1-6 h, and heating at a speed of 2-8 ℃/min in two sections.
5. The method for preparing the heterostructure yolk shell type double transition metal selenide composite material according to claim 1, wherein the organic ligand reagent is one or more of fumaric acid, benzoic acid, oxalic acid and pyrazine;
the reagents in S1 and S2 are one or more of deionized water, methanol, ethanol, N-dimethylformamide, N-diethylformamide, acetonitrile and acetone;
the precipitant comprises one or more of ammonium chloride, urea, sodium hydroxide and sodium carbonate.
6. Heterostructure yolk-shell double transition metal selenide composite material prepared by the preparation method according to any one of claims 1 to 5.
7. The heterostructure yolk-shell double transition metal selenide composite of claim 6, wherein the composite has a hollow yolk-eggshell structure having a particle size of 1 to 2 μm.
8. The use of the heterostructure yolk-shell double transition metal selenide composite material of claim 7 in preparing a negative electrode active material of a sodium ion battery.
9. The sodium ion battery is characterized by comprising an electrode plate, a counter electrode, a diaphragm and electrolyte, wherein the electrode plate is prepared by mixing the heterostructure yolk shell type double transition metal selenide composite material according to claim 7 with acetylene black and polyvinylidene fluoride according to the mass ratio of 5-7:1-2:1, the counter electrode is a sodium metal plate, the diaphragm is a glass fiber diaphragm, and the electrolyte is prepared by mixing 1 mol.L -1 Sodium hexafluorophosphate is dissolved in diethylene glycol methyl ether.
10. The sodium ion battery is characterized by comprising an electrode plate, a counter electrode, a diaphragm and electrolyte, wherein the electrode plate is prepared by mixing the heterostructure yolk shell type double transition metal selenide composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 5-7:1-2:1, the counter electrode is a sodium vanadium phosphate positive electrode material, the diaphragm is a glass fiber diaphragm, and the electrolyte is prepared by mixing 1 mol.L -1 Sodium hexafluorophosphate is dissolved in diethylene glycol methyl ether.
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