CN117154212A - Cobalt-based bimetallic selenide/graphene aerogel composite material, sodium ion battery negative plate, preparation method and application - Google Patents
Cobalt-based bimetallic selenide/graphene aerogel composite material, sodium ion battery negative plate, preparation method and application Download PDFInfo
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- CN117154212A CN117154212A CN202311223244.1A CN202311223244A CN117154212A CN 117154212 A CN117154212 A CN 117154212A CN 202311223244 A CN202311223244 A CN 202311223244A CN 117154212 A CN117154212 A CN 117154212A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 239000004964 aerogel Substances 0.000 title claims abstract description 69
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 56
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 53
- 239000010941 cobalt Substances 0.000 title claims abstract description 53
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 52
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims abstract description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- -1 cobalt diselenide-iron diselenide Chemical compound 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 229920003081 Povidone K 30 Polymers 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 18
- 239000010405 anode material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000002071 nanotube Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 229910002441 CoNi Inorganic materials 0.000 description 3
- 229910020521 Co—Zn Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910002521 CoMn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a cobalt-based bimetal selenide/graphene aerogel composite material, a sodium ion battery negative plate, a preparation method and application thereof, and can effectively improve the cycle performance and the capacitance of the sodium ion battery negative plate. The preparation method of the composite material comprises the following steps: step 1, adding metal salt and a dispersing agent into a solvent and continuously stirring to obtain a solution A; step 2, adding potassium hexacyanocobaltate into a solvent and continuously stirring to obtain a solution B; step 3, slowly dripping the solution A into the solution B, continuously stirring until the solution A and the solution B are uniformly mixed, and processing to obtain a complex precursor C; step 4, dispersing the C in a graphene oxide solution for ultrasonic treatment, and then freeze-drying to obtain a graphene oxide-coated complex precursor D; and 5, fully grinding and uniformly mixing the D and the selenium powder, then heating to 400-500 ℃ under a protective atmosphere, calcining for 2-3 h, and cooling to room temperature to obtain the cobalt-based bimetallic selenide/graphene aerogel composite material.
Description
Technical Field
The invention belongs to the technical field of new energy storage, and particularly relates to a cobalt-based bimetal selenide/graphene aerogel composite material, a sodium ion battery negative plate, a preparation method and application thereof.
Background
Climate warming and global warming have become serious problems facing all human beings, and are mainly the greenhouse effect caused by carbon dioxide emission. In recent years, china actively implements national strategy for climate change, adopts ways of adjusting industrial structures, optimizing energy structures and the like to save energy and improve energy efficiency. The research and development of new energy materials is an important problem for realizing carbon peak and carbon neutralization at present. Currently, lithium ion batteries are the main stream of development for many power batteries due to their excellent cycle performance and mature technology. The lithium is used as a key raw material and the strategic value is continuously highlighted due to the fact that the worldwide electric automobile is benefited. With this, the price of lithium resources is continuously increasing. As a potential alternative to lithium ion batteries in future energy storage systems, sodium ion batteries are therefore becoming increasingly attractive due to their high energy density and abundant sodium resources. Compared with lithium ion batteries, the radius of sodium ions is larger than that of lithium ions, and the molar mass is larger, so that the ion diffusion kinetics are slower, and the cathode material needs larger interlayer spacing. This results in the graphite negative electrode used in commercial lithium ion batteries not being well used in sodium ion batteries. Therefore, development of commercial sodium ion battery anode materials is becoming critical and urgent.
Among the reported anode materials, metal selenide is one of the most promising anode materials of sodium ion batteries at present, and has the advantages of good reversibility, small volume change, large theoretical capacity and the like. However, when the metal selenide is used as a negative electrode material, the problems of low ion/electron conductivity, low initial coulombic efficiency, poor cycle performance and the like exist, and the problems need to be solved.
Disclosure of Invention
The invention aims to solve the problems, and aims to provide a cobalt-based bimetal selenide/graphene aerogel composite material, a sodium ion battery negative plate, a preparation method and application thereof, which can effectively improve the cycle performance and the capacitance of the sodium ion battery negative plate.
In order to achieve the above object, the present invention adopts the following scheme:
< method for producing composite Material >
The invention provides a preparation method of a cobalt-based bimetallic selenide/graphene aerogel composite material, which comprises the following steps:
step 1, adding metal salt and a dispersing agent into a solvent and continuously stirring to obtain a solution A, wherein the ratio of the metal salt to the solvent=3-6 mmol to 50-60 mL;
step 2, adding potassium hexacyanocobaltate into a solvent and continuously stirring to obtain a solution B, wherein the solvent=3-6 mmol:50-60 mL of potassium hexacyanocobaltate, and the amount of the potassium hexacyanocobaltate is equal to that of the metal salt in the step 1;
step 3, slowly dripping the solution A into the solution B, continuously stirring until the solution A is uniformly mixed, standing, and centrifuging, washing and drying to obtain a complex precursor C;
step 4, dispersing the complex precursor C in a graphene oxide solution for ultrasonic treatment, and then freeze-drying to obtain a graphene oxide-coated complex precursor D;
and 5, fully grinding the complex precursor D and the selenium powder after mixing, uniformly mixing, heating to 400-500 ℃ under a protective atmosphere, calcining for 2-3 h, and cooling to room temperature to obtain the cobalt-based bimetallic selenide/graphene aerogel composite material.
Preferably, in the preparation method of the cobalt-based bimetallic selenide/graphene aerogel composite material provided by the invention, in the step 1, the metal salt is any one of soluble zinc salt, nickel salt, manganese salt or iron salt.
Preferably, in the preparation method of the cobalt-based bimetallic selenide/graphene aerogel composite material provided by the invention, in the step 1, the dispersing agent is sodium citrate or PVP-K30.
Preferably, in the preparation method of the cobalt-based bimetallic selenide/graphene aerogel composite material, in the step 1, metal salt and a dispersing agent are added into a solvent according to the mass ratio of 1:0.8-2.7; in the step 4, the concentration of the graphene oxide is 1.5-2.5 mg/ml, and the freeze drying condition is-80 ℃; in the step 5, the complex precursor D and selenium powder are mixed according to the mass ratio of 1:2.5-5, and then the mixture is placed in a tube furnace, and the temperature is raised to 400-500 ℃ at the heating rate of 1.5-3 ℃/min under the protection of hydrogen-argon mixed atmosphere.
Preferably, in the preparation method of the cobalt-based bimetallic selenide/graphene aerogel composite material provided by the invention, in the steps 1 and 2, the solvent is water, absolute ethyl alcohol or a mixture of the two in any proportion.
Preferably, in the preparation method of the cobalt-based bimetal selenide/graphene aerogel composite material provided by the invention, in the step 5, the cobalt-based bimetal selenide/graphene aerogel composite material is cobalt diselenide-iron diselenide CoSe with a heterostructure 2 -FeSe 2 @rGO, cobalt diselenide-nickel diselenide CoSe 2 -nise@rgo, cobalt diselenide-zinc selenide CoSe 2 -znse@rgo, cobalt diselenide-manganese diselenide CoSe 2 -any one of mnse@rgo.
< composite Material >
Further, the present invention also provides a cobalt-based bi-metal selenide/graphene aerogel composite prepared using the method described in < composite preparation method > above.
< method for producing negative electrode sheet >
Further, the invention also provides a preparation method of the sodium ion battery negative plate, which comprises the following steps:
step I, obtaining a cobalt-based bi-metal selenide/graphene aerogel composite material by adopting the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material according to any one of claims 1 to 6;
and II, uniformly mixing (70-80): (10-20): (60-80): (10-60) cobalt-based bimetallic selenide/graphene aerogel composite material, a conductive agent, a binder and an organic solvent, stirring for 20-30 hours, coating on a copper foil current collector, and carrying out vacuum drying to obtain the sodium ion battery negative electrode plate.
< negative plate >
Further, the invention also provides a sodium ion battery negative electrode sheet prepared by the method described in the above < negative electrode sheet preparation method >.
< application >
Further, the cobalt-based bimetallic selenide/graphene aerogel composite material is also applied to sodium ion batteries: preparing a cobalt-based bimetallic selenide/graphene aerogel composite material into an electrode slice, then taking the electrode slice as a working electrode, taking a sodium slice as a counter electrode, taking glass fiber as a diaphragm, and adopting 1mol/L NaClO of equal volumes of ethylene carbonate and dimethyl carbonate 4 Is an electrolyte, and is assembled into a CR2032 button sodium ion battery in a glove box filled with argon.
Effects and effects of the invention
The cobalt-based bimetallic selenide/graphene aerogel composite material prepared by the method can be used as an excellent negative electrode material of a sodium ion battery to prepare a negative electrode plate, has high specific capacity and cycle performance, is simple in process, good in reproducibility and easy to implement, and is suitable for mass production.
Specifically, cobalt-based bimetallic selenide/graphene aerogel composite negative electrode plate applied to sodium ion battery at 200mA g -1 After 100 circles of current, coSe 2 -FeSe 2 @rGO、CoSe 2 -NiSe@rGO、CoSe 2 -ZnSe@rGO、CoSe 2 The charging capacities of-MnSe@rGO are 784.5mAh g respectively -1 、579.3mAh g -1 、566.2mAh g -1 、515.7mAh g -1 。
Drawings
FIG. 1 shows CoSe obtained in accordance with the first embodiment of the present invention 2 -FeSe 2 Scanning electron microscope images of the graphene aerogel composite material;
FIG. 2 (a) is an electron microscope scanning image of a graphene oxide-coated CoNi-based complex D prepared in example two of the present invention;
FIG. 2 (b) shows CoSe obtained in accordance with the second embodiment of the present invention 2 -electron microscopy scanned images of nise@rgo composite material;
FIG. 3 shows CoSe prepared in accordance with example III of the present invention 2 -electron microscope scanning images of znse@rgo composite material;
FIG. 4 shows CoSe as an embodiment of the present invention 2 -FeSe 2 Transmission electron microscope image of @ rGO composite material;
FIG. 5 shows CoSe prepared in accordance with example IV of the present invention 2 -electron microscopy scanned images of mnse@rgo composite material;
FIG. 6 is an X-ray diffraction pattern of a cobalt-based bi-metal selenide/graphene aerogel composite prepared in accordance with an embodiment of the invention;
FIG. 7 is a graph showing the cycle performance of a cobalt-based bi-metal selenide/graphene aerogel composite negative electrode sheet prepared in the example of the invention and a negative electrode material of comparative example for a sodium ion battery at 200 mA/g.
Detailed Description
The cobalt-based bi-metal selenide/graphene aerogel composite material, the sodium ion battery negative electrode sheet and specific embodiments of the preparation method and the application related to the invention are described in detail below with reference to the accompanying drawings.
Example 1
In the first embodiment, the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material for the sodium ion battery and the negative electrode plate comprises the following steps:
(1) 0.76g (6 mmol) ferric chloride and 2g PVP-K30 are added into 50mL deionized water, and the mixture is continuously stirred until the mixture is completely dissolved, so as to obtain a solution A;
(2) 1.99g (6 mmol) of potassium hexacyanocobaltate was added to 50mL of deionized water and stirred continuously until all dissolved to give solution B;
(3) Slowly dripping the solution A into the solution B, continuously stirring, centrifuging, washing and drying after 24 hours to obtain a CoFe-based complex C;
(4) Dispersing 0.05g CoFe-based complex C in 33mL of graphene oxide solution with the concentration of 1.5mg/mL and carrying out ultrasonic treatment for 2 hours; then freeze-drying is carried out at the temperature of minus 80 ℃ to obtain a CoFe-based complex D wrapped by graphene oxide;
(5) Fully grinding 0.1g of complex precursor D and 0.3g of selenium powder in a mortar to uniformly mix the materials, then placing the materials in a tube furnace, calcining the materials for 3 hours at 450 ℃ under the mixed atmosphere of protective hydrogen and argon at the heating rate of 1.5 ℃/min, and naturally cooling the materials to room temperature to obtain solid powder which is cobalt diselenide-iron diselenide/graphene aerogel (CoSe) with a heterostructure 2 -FeSe 2 @ rGO) composite;
(6) CoSe is to 2 -FeSe 2 Uniformly mixing and stirring the @ rGO composite material, a conductive agent, a binder PVDF and an organic solvent according to a mass ratio of 80:10:10:80 for 24 hours, coating the mixture on a copper foil current collector, and performing vacuum drying to obtain the CoSe for the sodium ion battery 2 -FeSe 2 The @ rGO composite material negative plate.
Further, the above negative electrode sheet was used for assembling and performance testing of a button sodium ion battery (CR 2032):
(7) The CoSe obtained in the step (6) is processed 2 -FeSe 2 The @ rGO composite material negative plate is used for a sodium ion battery, the sodium plate is used as a counter electrode, a glass fiber filter membrane is used as a diaphragm, and 1mol/L NaClO of equal volume of ethylene carbonate and dimethyl carbonate is adopted 4 Is electrolyte filled with argonThe CR2032 button sodium ion battery is assembled in a glove box.
(8) The sodium ion battery assembled in the step (7) is controlled to be 100mA g within the voltage range of 0.01-3V -1 The current density of (2) is used for the first three times of charge-discharge activation. After activation, the voltage is in the range of 0.01-3V, 200mA g -1 Is subjected to charge-discharge cycle test.
< example two >
In the second embodiment, the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material for the sodium ion battery and the negative electrode sheet comprises the following steps:
(1) 0.79g (3 mmol) of nickel sulfate hexahydrate and 1g of PVP-K30 were added to 60mL of deionized water and stirred continuously until all dissolved to give solution A;
(2) 0.99g (3 mmol) of potassium hexacyanocobaltate was added to 50mL of deionized water and stirred continuously until all dissolved to give solution B;
(3) Slowly dripping the solution A into the solution B, continuously stirring, centrifuging, washing and drying after 24 hours to obtain a Co-Ni-based complex C;
(4) Dispersing 0.05g of Co-Ni based complex C in 33mL of graphene oxide solution with the concentration of 1.5mg/mL and carrying out ultrasonic treatment for 2 hours; then freeze-drying at-80 ℃ to obtain a CoNi-based complex D wrapped by graphene oxide;
(5) Fully grinding 0.15g of complex precursor D and 0.45g of selenium powder in a mortar to uniformly mix the materials, then placing the materials in a tube furnace, calcining the materials for 2 hours at 400 ℃ under the mixed atmosphere of protective hydrogen and argon at the heating rate of 1.5 ℃/min, and naturally cooling the materials to room temperature to obtain solid powder which is cobalt diselenide-nickel diselenide/graphene aerogel (CoSe) with a heterostructure 2 -NiSe 2 @ rGO) composite;
(6) CoSe is to 2 -NiSe 2 Uniformly mixing and stirring the @ rGO composite material, a conductive agent, a binder PVDF and an organic solvent according to a mass ratio of 80:10:10:80 for 24 hours, coating the mixture on a copper foil current collector, and performing vacuum drying to obtain the CoSe for the sodium ion battery 2 -NiSe 2 The @ rGO composite material negative plate.
Further, the above negative electrode sheet was used for assembling and testing the performance of the button sodium ion battery (CR 2032), and the method was the same as in example one.
Example III
In the third embodiment, the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material for the sodium ion battery and the negative electrode plate comprises the following steps:
(1) 1.15g (4 mmol) of zinc sulfate heptahydrate and 1g of PVP-K30 are added into 60mL of deionized water, and the mixture is continuously stirred until the mixture is completely dissolved, so as to obtain a solution A;
(2) 1.33g (4 mmol) of potassium hexacyanocobaltate was added to 60mL of deionized water and stirred continuously until all dissolved to give solution B;
(3) Slowly dripping the solution A into the solution B, continuously stirring, centrifuging, washing and drying for 24 hours to obtain a Co-Zn-based complex C;
(4) 0.05g of Co-Zn based complex C was dispersed in 20mL of 2.5mg/mL graphene oxide solution and sonicated for 2 hours; then freeze-drying is carried out at the temperature of minus 80 ℃ to obtain a Co-Zn-based complex D wrapped by graphene oxide;
(5) Fully grinding 0.1g of complex precursor D and 0.3g of selenium powder in a mortar to uniformly mix the materials, then placing the materials in a tube furnace, calcining the materials for 2 hours at 450 ℃ under the mixed atmosphere of protective hydrogen and argon at the heating rate of 2.5 ℃/min, and naturally cooling the materials to room temperature to obtain solid powder which is cobalt diselenide-zinc diselenide/graphene aerogel (CoSe) with a heterostructure 2 -znse@rgo) composite material;
(6) CoSe is to 2 Uniformly mixing and stirring the ZnSe@rGO composite material, a conductive agent, a binder PVDF and an organic solvent according to a mass ratio of 80:10:10:80 for 24 hours, coating the mixture on a copper foil current collector, and performing vacuum drying to obtain the CoSe for the sodium ion battery 2 -ZnSe@rGO composite negative electrode sheet.
Further, the above negative electrode sheet was used for assembling and testing the performance of the button sodium ion battery (CR 2032), and the method was the same as in example one.
Example IV
In a fourth embodiment, the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material for the sodium ion battery and the negative electrode sheet comprises the following steps:
(1) 1.27g (5 mmol) of manganese acetate and 2g of PVP-K30 were added to 60mL of deionized water and stirred continuously until all dissolved to give solution A;
(2) 1.66g (5 mmol) of potassium hexacyanocobaltate was added to 60mL of deionized water and stirred continuously until all dissolved to give solution B;
(3) Slowly dripping the solution A into the solution B, continuously stirring, centrifuging, washing and drying for 24 hours to obtain a CoMn-based complex C;
(4) Dispersing 0.05. 0.05g C in 20mL of 2.5mg/mL graphene oxide solution and performing ultrasonic treatment for 2 hours; then freeze-drying is carried out at the temperature of minus 80 ℃ to obtain a Co-Mn-based complex D wrapped by graphene oxide;
(5) Fully grinding 0.1g of complex precursor D and 0.25g of selenium powder in a mortar to uniformly mix the materials, then placing the materials in a tube furnace, calcining the materials for 3 hours at 500 ℃ at a heating rate of 2.5 ℃/min under a protective hydrogen-argon mixed atmosphere, and naturally cooling the materials to room temperature to obtain solid powder which is cobalt diselenide-manganese diselenide/graphene aerogel (CoSe) with a heterostructure 2 -mnse@rgo) composite material;
(6) CoSe is to 2 Uniformly mixing and stirring the MnSe@rGO composite material, a conductive agent, a binder PVDF and an organic solvent according to a mass ratio of 80:10:10:80 for 24 hours, coating the mixture on a copper foil current collector, and performing vacuum drying to obtain the CoSe for the sodium ion battery 2 -MnSe@rGO composite material negative electrode sheet.
Further, the above negative electrode sheet was used for assembling and testing the performance of the button sodium ion battery (CR 2032), and the method was the same as in example one.
Comparative example one ]
In the first comparative example, the present invention is compared with the preparation method scheme of the iron selenide-iron oxide nanotube/graphene aerogel composite anode material of the patent ZL 202122347395.9.
Firstly, preparing an iron selenide-iron oxide nanotube/graphene aerogel composite anode material by adopting the method of the patent ZL 202122347395.9:
1) 0.4162g of ferric chloride and 0.5327g of fumaric acid were added to a beaker containing 80ml of deionized water and stirred continuously at 800r/min until all dissolved.
2) Transferring the mixed aqueous solution in the step 1) into a 100ml high-pressure reaction kettle, then placing the mixture into an oven for hydrothermal treatment, and naturally cooling the mixture to room temperature after the mixture is kept at 70 ℃ for 24 hours; centrifugal separation is carried out at the rotating speed of 4000r/min, and ethanol and deionized water are used for washing for 3 times; finally, placing the precipitate into vacuum drying and drying at 80 ℃ to obtain the iron-based metal-organic framework nanorod;
3) Ultrasonically dispersing the product obtained in the step 2) in 2.5mg/ml graphene oxide solution for 1 hour; then placing the mixture in a freeze dryer, and keeping the mixture at the temperature of minus 80 ℃ for 2 days to obtain the graphene oxide coated iron-based metal organic framework nanorod;
4) Mixing the product obtained in the step 3) with selenium powder according to the following weight ratio of 1:4 mass ratio is respectively arranged at the downstream and the upstream of the porcelain boat, the temperature is kept at 300 ℃ for 1 hour at a heating rate of 3 ℃/min of hydrogen-argon mixed gas in a tube furnace, then the temperature is continuously raised to 500 ℃ and kept for 2 hours, and then the composite anode material of the iron selenide-iron oxide nano tube/graphene aerogel is naturally cooled to room temperature, so that the composite anode material of the iron selenide-iron oxide nano tube/graphene aerogel is obtained.
Then, assembling and performance testing of the button sodium ion battery (CR 2032) are carried out on the iron selenide-iron oxide nanotube/graphene aerogel composite anode material:
5) Uniformly mixing the iron selenide-iron oxide nanotube/graphene aerogel composite anode material obtained in the step 4), a conductive agent, a binder PVDF and an organic solvent according to a mass ratio of 80:10:10:80, stirring for 24 hours, coating the mixture on a copper foil current collector, and carrying out vacuum drying to obtain the iron selenide-iron oxide nanotube/graphene aerogel composite anode sheet for the sodium ion battery.
6) The composite material negative plate obtained in the step 5) is used for a sodium ion battery, the sodium plate is used as a counter electrode, a glass fiber filter membrane is used as a diaphragm, and 1mol/L NaClO of equal volume of ethylene carbonate and dimethyl carbonate is adopted 4 Is an electrolysis of a mixture ofThe solution was assembled into CR2032 button sodium ion battery in an argon filled glove box.
7) The sodium ion battery assembled in the step 6) is in the voltage range of 0.01-3V and 100mA g -1 The current density of (2) is used for the first three times of charge-discharge activation. After activation, the voltage is in the range of 0.01-3V, 200mA g -1 Is subjected to charge-discharge cycle test.
< comparative example two >
In the second comparative example, the present invention was compared with the nickel selenide-zinc selenide microsphere/graphene anode material having the patent application number CN2023103853378, and the preparation method and application scheme thereof.
In the same way as in comparative example one, nickel selenide-zinc selenide microsphere/graphene anode material was prepared according to CN2023103853378 method, and then the anode material was subjected to assembly and performance test of button sodium ion battery (CR 2032).
< analysis of Experimental data >
As shown in FIG. 1, coSe prepared in example one 2 -FeSe 2 Spherical particles with uniform morphology of graphene aerogel composite material and CoSe 2 -FeSe 2 The particles are wrapped inside the three-dimensional graphene sheet, and the particle size range is 1 μm.
As shown in fig. 2 (a), particles of the precursor CoNi-based complex D before calcination in the second embodiment, which have a regular cube shape, are uniformly distributed on a large graphene sheet; as shown in FIG. 2 (b), coSe obtained after calcination 2 The morphology of the NiSe@rGO composite material is that small graphene sheets are deposited on cubic particles to form an irregular cubic structure.
As shown in FIG. 3, coSe prepared in example III 2 The morphology of the ZnSe@rGO composite material is spherical particles uniformly wrapped by graphene sheets.
As shown in FIG. 4, coSe prepared in example four 2 The morphology of the MnSe@rGO composite material is that the graphene sheets wrap the cubic particles.
As shown in fig. 5, in embodiment one, the CoSe 2 -FeSe 2 The @ rGO composite material has obvious heterogeneous interface and is bimetallic seleniumThe periphery of the compound is wrapped with graphene. The self-assembled structure forms a special heterojunction with a built-in electric field, so that more surface reaction sites can be provided, and larger volume change can be relieved in the charge and discharge process; these properties are beneficial for improving the rate performance and cycling stability of SIBs.
As shown in fig. 6, in the X-ray diffraction pattern of the cobalt-based bi-metal selenide/graphene aerogel composite, there is one broad peak at 20 to 26 °, which overlaps with the diffraction peak position of graphene. In addition, each diffraction peak corresponds to the generation of the corresponding selenide, and the successful preparation of the material is further confirmed.
As shown in FIG. 7, the cobalt-based bi-metal selenide/graphene aerogel composite material negative electrode sheet prepared by the embodiment of the invention and the negative electrode material of comparative example are used for comparing the cycle performance of a sodium ion battery at 200mA/g, and the charging capacities after 100 cycles are 784.5mAh g respectively -1 、579.3mAh g -1 、566.2mAh g -1 、515.7mAh g -1 326.3mAh g -1 . It can be seen that the cobalt-based bi-metal selenide/graphene aerogel composite material of the invention has significantly improved post-cycling capacity compared to the iron selenide-iron oxide nanotube/graphene aerogel composite material.
Comparative sodium Electrical Property results of examples one to four and comparative example one the sodium ion batteries of examples one to four and comparative example one were shown in Table 1 below, table 1 below showing that at 200mA g -1 Charge and discharge tests were performed at current, first coulombic efficiency and capacity obtained at turn 100.
TABLE 1
As can be seen from Table 1, the cobalt-based bi-metal selenide/graphene aerogel composite negative electrode sheet of the invention was used for sodium ion batteries at 200mA g -1 Under the condition that the charging capacities after 100 circles of circulation are 784.5mAh g respectively -1 、579.3mAh g -1 、566.2mAh g -1 And 515.7mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific charge capacity of the iron selenide-iron oxide nanotube/graphene aerogel composite material of the comparative example I after 100 circles is 326.3mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific charge capacity of the nickel selenide-zinc selenide microsphere/graphene anode material of the second comparative example after 100 circles is 312.1mAh g -1 . It can be seen that the cobalt-based bimetallic selenide/graphene aerogel composite material has excellent specific capacity and cycle performance. Compared with the iron selenide-iron oxide nano tube/graphene aerogel composite material, the cobalt-based bimetallic selenide/graphene aerogel composite material has the advantage that the capacity after circulation is remarkably improved. Compared with the nickel selenide-zinc selenide microsphere/graphene composite material, the cobalt-based bimetal selenide/graphene aerogel composite material also has the remarkably improved capacity after circulation, and compared with the nickel selenide-zinc selenide microsphere/graphene composite material, the cobalt-based bimetal selenide/graphene aerogel composite material has the remarkably improved capacity after circulation.
The above embodiments are merely illustrative of the technical solutions of the present invention. The cobalt-based bi-metal selenide/graphene aerogel composite material, the sodium ion battery negative electrode sheet, the preparation method and the application thereof are not limited to the content described in the above embodiments, but the scope defined by the claims. Any modifications, additions or equivalent substitutions made by those skilled in the art based on this embodiment are within the scope of the invention as claimed in the claims.
Claims (10)
1. The preparation method of the cobalt-based bimetallic selenide/graphene aerogel composite material is characterized by comprising the following steps of:
step 1, adding metal salt and a dispersing agent into a solvent and continuously stirring to obtain a solution A, wherein the ratio of the metal salt to the solvent=3-6 mmol to 50-60 mL;
step 2, adding potassium hexacyanocobaltate into a solvent and continuously stirring to obtain a solution B, wherein the solvent=3-6 mmol:50-60 mL of potassium hexacyanocobaltate, and the amount of the potassium hexacyanocobaltate is equal to that of the metal salt in the step 1;
step 3, slowly dripping the solution A into the solution B, continuously stirring until the solution A is uniformly mixed, standing, and centrifuging, washing and drying to obtain a complex precursor C;
step 4, dispersing the complex precursor C in a graphene oxide solution for ultrasonic treatment, and then freeze-drying to obtain a graphene oxide-coated complex precursor D;
and 5, fully grinding the complex precursor D and the selenium powder after mixing, uniformly mixing, heating to 400-500 ℃ under a protective atmosphere, calcining for 2-3 h, and cooling to room temperature to obtain the cobalt-based bimetallic selenide/graphene aerogel composite material.
2. The method for preparing the cobalt-based double-metal selenide/graphene aerogel composite material according to claim 1, wherein the method comprises the following steps:
in the step 1, the metal salt is any one of soluble zinc salt, nickel salt, manganese salt or ferric salt.
3. The method for preparing the cobalt-based double-metal selenide/graphene aerogel composite material according to claim 1, wherein the method comprises the following steps:
wherein, in the step 1, the dispersing agent is sodium citrate or PVP-K30.
4. The method for preparing the cobalt-based double-metal selenide/graphene aerogel composite material according to claim 1, wherein the method comprises the following steps:
wherein, in the step 1, metal salt and dispersant are added into solvent according to the mass ratio of 1:0.8-2.7;
in the step 5, the complex precursor D and selenium powder are mixed according to the mass ratio of 1:2.5-5, and then the mixture is placed in a tube furnace, and the temperature is raised to 400-500 ℃ at the heating rate of 1.5-3 ℃/min under the protection of hydrogen-argon mixed atmosphere.
5. The method for preparing the cobalt-based double-metal selenide/graphene aerogel composite material according to claim 1, wherein the method comprises the following steps:
in the steps 1 and 2, the solvent is water, absolute ethyl alcohol or a mixture of the water and the absolute ethyl alcohol in any proportion.
6. The method for preparing the cobalt-based double-metal selenide/graphene aerogel composite material according to claim 1, wherein the method comprises the following steps:
wherein in the step 5, the cobalt-based bimetallic selenide/graphene aerogel composite material is cobalt diselenide-iron diselenide CoSe 2 -FeSe 2 @rGO, cobalt diselenide-nickel diselenide CoSe 2 -nise@rgo, cobalt diselenide-zinc selenide CoSe 2 -znse@rgo, cobalt diselenide-manganese diselenide CoSe 2 -any one of mnse@rgo.
7. The cobalt-based bimetallic selenide/graphene aerogel composite material is characterized in that:
a method of preparing a cobalt-based bi-metal selenide/graphene aerogel composite according to any one of claims 1 to 6.
8. The preparation method of the sodium ion battery negative plate is characterized by comprising the following steps:
step I, obtaining a cobalt-based bi-metal selenide/graphene aerogel composite material by adopting the preparation method of the cobalt-based bi-metal selenide/graphene aerogel composite material according to any one of claims 1 to 6;
and II, uniformly mixing (70-80): (10-20): (60-80): (10-60) cobalt-based bimetallic selenide/graphene aerogel composite material, a conductive agent, a binder and an organic solvent, stirring for 20-30 hours, coating on a copper foil current collector, and carrying out vacuum drying to obtain the sodium ion battery negative electrode plate.
9. Sodium ion battery negative plate, its characterized in that:
the method for preparing the sodium ion battery negative plate according to claim 7.
10. Use of the cobalt-based bi-metal selenide/graphene aerogel composite of any one of claims 1 to 6 in sodium ion batteries, characterized in that:
preparing a cobalt-based bimetallic selenide/graphene aerogel composite material into an electrode slice, then taking the electrode slice as a working electrode, taking a sodium slice as a counter electrode, taking glass fiber as a diaphragm, and adopting 1mol/L NaClO of equal volumes of ethylene carbonate and dimethyl carbonate 4 Is an electrolyte, and is assembled into a CR2032 button sodium ion battery in a glove box filled with argon.
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