CN114380341A - Preparation method of sodium ion iron cobalt nickel sulfide nanosheet - Google Patents
Preparation method of sodium ion iron cobalt nickel sulfide nanosheet Download PDFInfo
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- CN114380341A CN114380341A CN202111493132.9A CN202111493132A CN114380341A CN 114380341 A CN114380341 A CN 114380341A CN 202111493132 A CN202111493132 A CN 202111493132A CN 114380341 A CN114380341 A CN 114380341A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRWBTLYPUWBLTA-UHFFFAOYSA-N cobalt;iron;sulfanylidenenickel Chemical compound [Fe].[Co].[Ni]=S KRWBTLYPUWBLTA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical group [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 11
- -1 nickel potassium hydride Chemical group 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 3
- ZJHHBANSOJOTAN-UHFFFAOYSA-J O.O.O.O.[Co+2].C(C)(=O)[O-].[Co+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound O.O.O.O.[Co+2].C(C)(=O)[O-].[Co+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] ZJHHBANSOJOTAN-UHFFFAOYSA-J 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract 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 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 30
- 229910052976 metal sulfide Inorganic materials 0.000 description 13
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 4
- 229910002545 FeCoNi Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229940091258 selenium supplement Drugs 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KTLOQXXVQYUCJU-UHFFFAOYSA-N [Cu].[Cu].[Se] Chemical compound [Cu].[Cu].[Se] KTLOQXXVQYUCJU-UHFFFAOYSA-N 0.000 description 1
- TWUIETAITAHTIX-UHFFFAOYSA-N [NiH2].[K] Chemical group [NiH2].[K] TWUIETAITAHTIX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a sodium ion iron cobalt nickel sulfide nanosheet, which comprises the following steps: adding soluble potassium salt into deionized water, and stirring until the soluble potassium salt is completely dissolved to obtain a solution A; adding soluble cobalt salt, soluble ferric salt and trisodium citrate into deionized water, and stirring until the soluble cobalt salt, the soluble ferric salt and the trisodium citrate are completely dissolved to obtain a solution B; adding the solution A into the solution B, stirring and standing at room temperature, performing suction filtration to collect a sample, washing with deionized water and ethanol, and performing vacuum drying to obtain a powder product; and (5) carrying out secondary annealing and vulcanization treatment on the powder product obtained in the step S3 to finally obtain the FeS/CoS/NiS nanosheet. The iron-cobalt-nickel sulfide nanosheet prepared by the method has a porous structure, can promote the full permeation of electrolyte, and effectively relieves the volume change of sodium in the circulation process. The invention can be better applied to the cathode material of the sodium-ion battery and has better implementability and wide popularization.
Description
Technical Field
The invention relates to the technical field of preparation of sodium ion battery materials, in particular to a preparation method of a sodium ion iron cobalt nickel sulfide nanosheet.
Background
With the progress of the twenty-first century, the global energy consumption is continuously accelerated, and the worldwide problems of global warming, environmental pollution, resource shortage and the like are caused by the massive exploitation of fossil energy such as coal, petroleum, natural gas and the like, so that the development of renewable clean energy is imminent. The existing natural renewable energy sources such as tidal energy, solar energy, wind energy and the like have the characteristics of intermittency, instability and the like, and the clean energy sources can be utilized only by storing the clean energy sources by means of an energy storage device. The secondary battery has the advantages of high specific energy, long cycle life, no memory effect, no pollution and the like, the lithium ion battery is developed well since the lithium ion battery is used for the first time in the 90 th 20 th century, the global lithium content is insufficient and uneven, and meanwhile, the lithium ion battery has many safety problems, so that the development of a new electrochemical energy storage technology with low cost and high performance is a necessary trend. Compared with lithium resources, the sodium storage on the earth is very rich and easy to obtain, meanwhile, sodium and lithium are in the same main group and have similar chemical characteristics and rich content, and the working principle of a sodium ion battery is almost the same as that of a lithium ion battery, so that the sodium ion battery is expected to replace the lithium ion battery as large-scale power grid energy storage. The sodium ion battery mainly comprises a positive electrode, a diaphragm, a negative electrode and electrolyte, and is a recyclable charge-discharge battery in which sodium ions are reversibly inserted and extracted in the positive electrode and the negative electrode in the battery, wherein the positive electrode material influences the capacity and the cyclicity of the battery. In order to improve the electrochemical performance of sodium ion batteries, research on metal sulfide materials of sodium ion batteries has received extensive attention from numerous scholars in recent years.
In the prior art, a copper selenide material is used as a cathode material of a sodium ion battery, and the cathode material of the sodium ion battery is obtained by combining two means of nanostructure design and intercalation of intercalation agent molecules. But the proportion of the synthesized copper selenide is not easy to control, if enough selenium participates in the reaction, bivalent copper selenide can be formed, and cuprous selenide can be easily formed, and the condition of the synthesized copper selenide is also difficult to control, a large amount of foam can be generated when hexadecyl trimethyl ammonium chloride in the intercalation agent is rapidly stirred, and elemental selenium can be separated out when sodium selenite in the selenium source meets a strong oxidant.
In the prior art, an electrochemical method is also adopted to compound iron phosphide nanosheets and a biomass carbon film to obtain the iron phosphide/biomass carbon integrated electrode without a binder. However, the raw material graphite flake is expensive, the alkaline solution in the prepared biomass carbon film is easy to react with the acidic solution to reduce the concentration of the acid solution, the operation steps for preparing the iron phosphide/biomass carbon by adopting the electrochemical method are complicated, the method is not suitable for large-scale preparation, the oxalic acid material can be decomposed to generate toxic carbon monoxide under the condition of high temperature, the oxalic acid is difficult to treat and has great harm to the environment, and the prepared iron phosphide nanosheet and biomass carbon composite material has short cycle life and is not easy to industrialize.
Therefore, a new preparation process which is simple and easy to operate, has stable synthetic product and high yield, can reduce the generation of by-products, has small harm to human bodies and environment from raw materials and is easy to industrialize is needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a sodium ion iron cobalt nickel sulfide nanosheet.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a sodium ion iron cobalt nickel sulfide nanosheet is characterized in that the iron cobalt nickel sulfide nanosheet is of an array arrangement structure, is uniform in size, and is 2-3 mu m in size.
Preferably, the preparation method comprises the following steps:
s1, adding soluble potassium salt into deionized water, and stirring until the potassium salt is completely dissolved to obtain a solution A;
s2, adding soluble cobalt salt, soluble ferric salt and trisodium citrate into deionized water, and stirring until the soluble cobalt salt, the soluble ferric salt and the trisodium citrate are completely dissolved to obtain a solution B;
s3, adding the solution A into the solution B, stirring and standing at room temperature, performing suction filtration to collect a sample, washing with deionized water and ethanol, and performing vacuum drying to obtain a powder product;
and S4, carrying out secondary annealing and vulcanizing treatment on the powder product obtained in the step S3 to finally obtain the FeS/CoS/NiS nanosheet.
Preferably, the molar concentration of the soluble potassium salt is 20 mM.
Preferably, the mol ratio of the soluble cobalt salt to the soluble iron salt to the trisodium citrate is 1:1: 0.75.
Preferably, the soluble potassium salt is potassium nickel hydride; the soluble cobalt salt cobalt acetate tetrahydrate; the soluble iron salt is ferric acetate tetrahydrate.
Preferably, the stirring time in the step S3 is 30 min; the vacuum drying is specifically drying for 5 hours at the temperature of 60-80 ℃.
Preferably, the volume ratio of the solution a to the solution B in the step S3 is: 1:1.
Preferably, the secondary annealing and vulcanizing treatment in step S4 is specifically: heating the powder product to 500-680 ℃ in the nitrogen atmosphere, and preserving the heat for 1-2 h; after annealing treatment, the powder sample is heated to 680 ℃ under the nitrogen atmosphere, and the temperature is kept for 1-2 h.
Preferably, the secondary annealing and vulcanizing treatment in step S4 is specifically: heating the powder product to 60 ℃ in a nitrogen atmosphere, and keeping the temperature for 2 h; after annealing treatment, the powder sample is heated to 600 ℃ in the nitrogen atmosphere and is kept warm for 2 h.
Preferably, the temperature rise rate is 1-3 ℃/min.
The invention has the beneficial effects that:
1) the method adopts soluble cobalt salt and soluble ferric salt, and brings direct effects that ternary metal sulfide precursor nanosheets are generated, the nanosheets are not easy to generate by using hexadecyl trimethyl ammonium chloride, and indirect effects that when the prepared electrode material is used as a negative electrode material of a sodium ion battery, the electrochemical performance of an electrode prepared by using the soluble cobalt salt and the soluble ferric salt is better, and stable nanosheets are generated because cobalt ions of the soluble cobalt salt and iron ions of the soluble ferric salt are more easy to participate in a vulcanization reaction;
2) the ternary metal sulfide nanosheets prepared by the method are orderly arranged in array, coated by the carbon layer, rough in surface and high in specific surface area, and when the ternary metal sulfide nanosheets are used as a negative electrode material of a sodium ion battery, the embedding and the separation of sodium ions are facilitated, the volume expansion caused in the charging and discharging process is better relieved, the stability of the nanosheet structure is maintained, the electrochemical performance of the sodium ion battery is greatly improved, and the specific capacity of the battery is improved due to the synergistic effect of multiple metals, so that the production cost can be well reduced;
3) the preparation method has the advantages of low price of raw materials, environmental friendliness, simple preparation process and easy implementation. The ternary metal sulfide prepared by the method has the advantages of strong electrochemical activity, ultra-long cycle life, stable production, high yield and convenience for industrial mass production. The prepared iron-cobalt-nickel sulfide nanosheet has a porous structure, can promote full permeation of electrolyte, and effectively relieves the volume change of sodium in the circulation process. The invention can be better applied to the cathode material of the sodium-ion battery and has better implementability and wide popularization.
Drawings
FIG. 1 is a scanning electron micrograph of FeCoNi sulfide prepared according to example 1 of the present invention, FIGS. 1(a) and 1(b) are scanning electron micrographs at low magnification and FIG. 1(c) is at high magnification;
FIG. 2 is a cyclic voltammogram of FeCoNi sulfide prepared in example 1 of the present invention;
FIG. 3 is a graph of the cycle performance of Fe-Co-Ni sulfide prepared in example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of Fe-Co-Ni sulfide prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, dissolving 8mmol of nickel potassium hydride in 400ml of deionized water, and magnetically stirring until the nickel potassium hydride is completely dissolved to obtain a solution A; and respectively dissolving 4mmol of cobalt acetate tetrahydrate, 4mmol of ferric acetate tetrahydrate and 3mmol of trisodium citrate in 400ml of deionized water, magnetically stirring the solution in the same way, and obtaining a solution B after the solution is completely dissolved. And secondly, adding the solution A into the solution B, fully stirring for 30 minutes at room temperature, standing, performing suction filtration to collect a sample, washing the sample with deionized water and ethanol for 3 times, and drying the sample in a vacuum drying oven at 60 ℃ for 5 hours to obtain dry powder. And finally, placing the powder in a tubular furnace, introducing nitrogen protective gas with the heating rate of 3 ℃/min, heating to 600 ℃, preserving heat for 2 hours, calcining, heating to 600 ℃ in the tubular furnace with the heating rate of 3 ℃/min, preserving heat for 2 hours, and vulcanizing a sample to obtain the ternary metal sulfide FeS/CoS/NiS.
Example 2
Firstly, dissolving 4mmol of nickel potassium hydride in 200ml of deionized water, and magnetically stirring until the nickel potassium hydride is completely dissolved to obtain a solution A; then 2mmol of cobalt acetate tetrahydrate, 2mmol of ferric acetate tetrahydrate and 1.5mmol of trisodium citrate are respectively dissolved in 200ml of deionized water, and the solution B is obtained after the cobalt acetate tetrahydrate, the ferric acetate tetrahydrate and the trisodium citrate are completely dissolved by the same magnetic stirring. And secondly, adding the solution A into the solution B, fully stirring for 30 minutes at room temperature, standing, performing suction filtration to collect a sample, washing the sample with deionized water and ethanol for 3 times, and drying the sample in a vacuum drying oven at 80 ℃ for 5 hours to obtain dry powder. And finally, placing the powder in a tubular furnace, introducing nitrogen protective gas with the heating rate of 2 ℃/min, heating to 600 ℃, preserving heat for 2 hours, calcining, heating to 600 ℃ in the tubular furnace with the heating rate of 2 ℃/min, preserving heat for 2 hours, and vulcanizing a sample to obtain the ternary metal sulfide FeS/CoS/NiS.
Example 3
Firstly, dissolving 8mmol of nickel potassium hydride in 400ml of deionized water, and magnetically stirring until the nickel potassium hydride is completely dissolved to obtain a solution A; and respectively dissolving 4mmol of cobalt acetate tetrahydrate, 4mmol of ferric acetate tetrahydrate and 3mmol of trisodium citrate in 400ml of deionized water, magnetically stirring the solution in the same way, and obtaining a solution B after the solution is completely dissolved. And secondly, adding the solution A into the solution B, fully stirring for 30 minutes at room temperature, standing, performing suction filtration to collect a sample, washing the sample with deionized water and ethanol for 3 times, and drying the sample in a vacuum drying oven at 70 ℃ for 5 hours to obtain dry powder. And finally, placing the powder in a tubular furnace, introducing nitrogen protective gas with the heating rate of 3 ℃/min, heating to 500 ℃, preserving heat for 1 hour, calcining, heating to 500 ℃ in the tubular furnace with the heating rate of 3 ℃/min, preserving heat for 1 hour, and vulcanizing a sample to obtain the ternary metal sulfide FeS/CoS/NiS.
Example 4
Firstly, dissolving 8mmol of nickel potassium hydride in 400ml of deionized water, and magnetically stirring until the nickel potassium hydride is completely dissolved to obtain a solution A; and respectively dissolving 4mmol of cobalt acetate tetrahydrate, 4mmol of ferric acetate tetrahydrate and 3mmol of trisodium citrate in 400ml of deionized water, magnetically stirring the solution in the same way, and obtaining a solution B after the solution is completely dissolved. And secondly, adding the solution A into the solution B, fully stirring for 30 minutes at room temperature, standing, performing suction filtration to collect a sample, washing the sample with deionized water and ethanol for 3 times, and drying the sample in a vacuum drying oven at 80 ℃ for 5 hours to obtain dry powder. And finally, placing the powder in a tubular furnace, introducing nitrogen protective gas with the heating rate of 1 ℃/min, heating to 680 ℃, preserving heat for 2 hours, calcining, heating to 680 ℃ in the tubular furnace with the heating rate of 1 ℃/min, preserving heat for 2 hours, and vulcanizing a sample to obtain the ternary metal sulfide FeS/CoS/NiS.
As shown in fig. 1, it is a scanning electron micrograph of the iron cobalt nickel sulfide prepared in example 1 under low magnification and high magnification, fig. 4 is an X-ray diffraction pattern of the iron cobalt nickel sulfide, and the positions and intensities of the diffraction peaks in fig. 4 correspond to the cards in fig. 1 one to one, which indicates that the product is the ternary metal sulfide FeS/CoS/NiS. Diffraction peaks at 30.7 °, 34.7 ° and 54.6 ° correspond to the 200, 201 and 220 planes of FeS, respectively, diffraction peaks at 34.7 °, 35.2 ° and 46.9 ° correspond to the 100, 101 and 102 planes of CoS, respectively, and diffraction peaks at 30.1 °, 34.7 ° and 53.5 ° correspond to the 100, 101 and 110 planes of NiS, respectively.
FIG. 2 is a cyclic voltammogram of FeCoNi sulfide prepared in example 1, the first cycle of the oxidation peaks are at 1.48, 1.73V and 1.96V, and the first cycle of the oxidation peaks are at 0.64V and 1.21V, respectively, the reduction peaks. The decrease in the intensity of the peak and the shift in the peak can be clearly seen in the second cycle, suggesting the formation of an SEI film, and the CV curves of the second and third cycles almost coincide, indicating good reversibility of the electrode. The cycling performance is shown in FIG. 3, from which it can be seen that the electrode still has a specific capacity of 573.22mAh/g over 50 cycles at a current density of 0.1A/g. Indicating that the electrode has good cycling stability.
The invention uses cobalt acetate tetrahydrate and ferric acetate tetrahydrate to replace hexadecyltrimethylammonium chloride materials, which brings direct effect of generating ternary metal sulfide precursor nanosheets, ensures that the nanosheets are not easy to generate by using the hexadecyltrimethylammonium chloride, and has indirect effect of enabling the prepared electrode material to be used as a cathode material of a sodium ion battery, and the electrode prepared by using the cobalt acetate tetrahydrate and the ferric acetate tetrahydrate has better electrochemical performance because the cobalt ions of the cobalt acetate tetrahydrate and the ferric ions of the ferric acetate tetrahydrate are easier to participate in a vulcanization reaction to generate stable nanosheets. In addition, cobalt acetate tetrahydrate and ferric acetate tetrahydrate are adopted to replace hexadecyltrimethylammonium chloride, the method is environment-friendly, the precursor is prepared by simple coprecipitation, the synthesis method is simple and convenient, the FeS/CoS/NiS sample is obtained by two-step annealing and vulcanization, the generation of byproducts can be effectively reduced, the yield of the sample is high, and the method is beneficial to large-scale industrial production.
The ternary metal sulfide nanosheets prepared by the method have the advantages of regular array arrangement, uniform size of about 2-3 microns, carbon layer coating outside, rough surface and high specific surface area, are favorable for embedding and separating sodium ions when being used as a negative electrode material of a sodium ion battery, better relieve volume expansion caused in the charging and discharging process, keep the stability of the nanosheet structure, greatly improve the electrochemical performance of the sodium ion battery, improve the specific capacity of the battery due to the synergistic effect of multiple metals and can well reduce the production cost.
The preparation raw materials of the invention have low price, are environment-friendly, and have simple preparation process and easy implementation. The ternary metal sulfide prepared by the method has the advantages of strong electrochemical activity, ultra-long cycle life, stable production, high yield and convenience for industrial mass production. The prepared iron-cobalt-nickel sulfide nanosheet has a porous structure, can promote full permeation of electrolyte, and effectively relieves the volume change of sodium in the circulation process. The invention can be better applied to the cathode material of the sodium-ion battery and has better implementability and wide popularization.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the sodium ion iron cobalt nickel sulfide nanosheet is characterized in that the iron cobalt nickel sulfide nanosheet is of an array arrangement structure, is uniform in size, and is 2-3 mu m in size.
2. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 1, wherein: the preparation method comprises the following steps:
s1, adding soluble potassium salt into deionized water, and stirring until the potassium salt is completely dissolved to obtain a solution A;
s2, adding soluble cobalt salt, soluble ferric salt and trisodium citrate into deionized water, and stirring until the soluble cobalt salt, the soluble ferric salt and the trisodium citrate are completely dissolved to obtain a solution B;
s3, adding the solution A into the solution B, stirring and standing at room temperature, performing suction filtration to collect a sample, washing with deionized water and ethanol, and performing vacuum drying to obtain a powder product;
and S4, carrying out secondary annealing and vulcanizing treatment on the powder product obtained in the step S3 to finally obtain the FeS/CoS/NiS nanosheet.
3. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the molar concentration of the soluble potassium salt is 20 mM.
4. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the mol ratio of the soluble cobalt salt to the soluble ferric salt to the trisodium citrate is 1:1: 0.75.
5. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the soluble potassium salt is nickel potassium hydride; the soluble cobalt salt cobalt acetate tetrahydrate; the soluble iron salt is ferric acetate tetrahydrate.
6. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the stirring time in the step S3 is 30 min; the vacuum drying is specifically drying for 5 hours at the temperature of 60-80 ℃.
7. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the volume ratio of the solution A to the solution B in the step S3 is as follows: 1:1.
8. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 2, wherein: the secondary annealing and vulcanizing treatment in the step S4 specifically includes: heating the powder product to 500-680 ℃ in the nitrogen atmosphere, and preserving the heat for 1-2 h; after annealing treatment, the powder sample is heated to 680 ℃ under the nitrogen atmosphere, and the temperature is kept for 1-2 h.
9. The method for preparing a sodium ion ferrocobalnickel sulfide nanosheet as claimed in claim 8, wherein: the secondary annealing and vulcanizing treatment in the step S4 specifically includes: heating the powder product to 60 ℃ in a nitrogen atmosphere, and keeping the temperature for 2 h; after annealing treatment, the powder sample is heated to 600 ℃ in the nitrogen atmosphere and is kept warm for 2 h.
10. The method for preparing sodium ion ferrocobalnickel sulfide nanosheets according to claim 8 or 9, wherein: the heating rate is 1-3 ℃/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899526A (en) * | 2018-07-11 | 2018-11-27 | 中国科学院宁波材料技术与工程研究所 | A kind of transient metal sulfide electrode material and preparation method thereof and solid lithium battery |
| CN111268734A (en) * | 2020-02-13 | 2020-06-12 | 广州大学 | Transition metal sulfide nanosheet and preparation method and application thereof |
| CN112436145A (en) * | 2020-11-16 | 2021-03-02 | 长沙理工大学 | Preparation method and application of MOF-74 derived carbon-coated cobalt-nickel bimetallic sulfide for sodium ion battery negative electrode |
| CN112952064A (en) * | 2021-03-22 | 2021-06-11 | 中国民用航空飞行学院 | Lithium ion ternary nanosheet and preparation method and application thereof |
-
2021
- 2021-12-08 CN CN202111493132.9A patent/CN114380341A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899526A (en) * | 2018-07-11 | 2018-11-27 | 中国科学院宁波材料技术与工程研究所 | A kind of transient metal sulfide electrode material and preparation method thereof and solid lithium battery |
| CN111268734A (en) * | 2020-02-13 | 2020-06-12 | 广州大学 | Transition metal sulfide nanosheet and preparation method and application thereof |
| CN112436145A (en) * | 2020-11-16 | 2021-03-02 | 长沙理工大学 | Preparation method and application of MOF-74 derived carbon-coated cobalt-nickel bimetallic sulfide for sodium ion battery negative electrode |
| CN112952064A (en) * | 2021-03-22 | 2021-06-11 | 中国民用航空飞行学院 | Lithium ion ternary nanosheet and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘沛静: ""一步法"合成NiCo_2S_4纳米阵列高性能能量存储器件电极的研究", 《材料开发与应用》 * |
| 肖成伟, 机械工业出版社 * |
| 郑永军: ""金属硫化物及其杂化材料的可控制备与储钠/储钾性能研究"", 《中国知网》 * |
| 马艳梅: "钠离子电池硫化物负极材料的研究进展", 《储能科学与技术》 * |
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