CN111668458A - Preparation method of cobalt sulfide/carbon composite positive electrode material, aluminum ion battery positive electrode and aluminum ion battery - Google Patents
Preparation method of cobalt sulfide/carbon composite positive electrode material, aluminum ion battery positive electrode and aluminum ion battery Download PDFInfo
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- CN111668458A CN111668458A CN201910164842.3A CN201910164842A CN111668458A CN 111668458 A CN111668458 A CN 111668458A CN 201910164842 A CN201910164842 A CN 201910164842A CN 111668458 A CN111668458 A CN 111668458A
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- positive electrode
- cobalt sulfide
- sulfide
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- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 title claims description 29
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 48
- 239000010941 cobalt Substances 0.000 claims abstract description 56
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 56
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000010406 cathode material Substances 0.000 claims abstract description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010405 anode material Substances 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000005987 sulfurization reaction Methods 0.000 abstract description 3
- -1 aluminum ion Chemical class 0.000 description 38
- 238000001035 drying Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 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
- 239000006258 conductive agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- DAYYOITXWWUZCV-UHFFFAOYSA-L cobalt(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O DAYYOITXWWUZCV-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a cobalt sulfide/carbon composite anode material, an aluminum ion battery anode and an aluminum ion battery, comprising the following steps of: respectively dissolving a cobalt source and alkyl substituted imidazole in a solvent according to a preset proportion to form a solution, and then mixing the two solutions to obtain a cobalt-containing organic metal framework material; and (3) preserving the heat of the cobalt-containing organic metal framework material and a sulfur source for a period of time at a preset temperature, and cooling to room temperature to obtain the cobalt sulfide/carbon composite cathode material. According to the invention, the cobalt-containing organic metal framework material with the sheet structure is subjected to sulfurization treatment by the cobalt-containing organic metal framework material and a sulfur source, so that a structure in which cobalt sulfide is uniformly dispersed in a carbon framework can be formed in situ, namely, the carbon-coated cobalt sulfide/carbon composite anode material is formed.
Description
Technical Field
The invention relates to the technical field of aluminum ion batteries, in particular to a preparation method of a cobalt sulfide/carbon composite positive electrode material, an aluminum ion battery positive electrode and an aluminum ion battery.
Background
The aluminum secondary battery has the characteristics of large energy, low cost, light weight, small volume, environmental protection, safety, stability, high cost performance and the like, and is a renewable new energy source which can be recycled and continuously developed. The metal aluminum is cheap and easy to obtain and recover, and the aluminum is the metal element with the highest content on the earth; the aluminum is used as a negative electrode material of the aluminum ion battery, the specific energy is very high, the theoretical electrochemical specific capacity can reach 2980mAh/g, and the aluminum is second to lithium in metal elements; the theoretical volumetric specific capacity of the aluminum can reach 8050mAh/cm3And is higher than most battery cathode materials in the prior art. Because the cathode material of the aluminum ion battery has higher capacity, correspondingly, the anode material of the aluminum ion battery also has higher capacity, and can be matched with the cathode to prepare the aluminum ion battery with high energy density. Therefore, the positive electrode material is a key component of the novel aluminum ion battery and is a main factor determining the electrochemical performance of the novel aluminum ion battery. The transition metal sulfide has excellent characteristics of good conductivity, large capacitance and the like, so that the transition metal sulfide becomes a novel aluminum ion battery positive electrode material with high competitiveness. However, Al generated in the electrode reaction of the transition metal sulfide2S3And the intermediate products can be dissolved in the electrolyte, so that the capacity of the aluminum ion battery is seriously attenuated in the charging and discharging processes.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a cobalt sulfide/carbon composite positive electrode material, an aluminum ion battery positive electrode and an aluminum ion battery, and aims to solve the problems that the structural stability and the electrical conductivity of the conventional positive electrode material of the aluminum ion battery are poor, and an active substance of the positive electrode material is easily dissolved in an electrolyte in a circulation process.
In a first aspect, the invention provides a preparation method of a cobalt sulfide/carbon composite cathode material, which comprises the following steps: step 1, respectively dissolving a cobalt source and alkyl substituted imidazole in a solvent according to a preset proportion to form a solution, then mixing the two solutions, standing and settling, and processing to obtain a cobalt-containing organic metal framework material; and 2, preserving the temperature of the cobalt-containing organic metal framework material and a sulfur source at a first preset temperature for a period of time, cooling to room temperature, and treating to obtain the cobalt sulfide/carbon composite anode material.
Further, the preparation method of the cobalt sulfide/carbon composite cathode material further comprises a step 3 of heating the cobalt sulfide/carbon composite cathode material to a second preset temperature which is not lower than the first preset temperature under an inert protective atmosphere, performing heat treatment at the second preset temperature for a period of time, and then cooling the cobalt sulfide/carbon composite cathode material.
Further, in the preparation method of the cobalt sulfide/carbon composite cathode material, the inert shielding gas is one or more of nitrogen, argon, helium and neon, and the solvent is one or more of methanol, ethanol and water.
Further, in the preparation method of the cobalt sulfide/carbon composite cathode material, the cobalt source is at least one of cobalt nitrate, cobalt sulfate and cobalt chloride; and/or the alkyl substituted imidazole is at least one of 2-methylimidazole, 2-ethylimidazole and 1, 2-dimethylimidazole; and/or the sulfur source is at least one of thioacetamide, thiourea and sublimed sulfur.
Further, in the above method for preparing a cobalt sulfide/carbon composite positive electrode material, the molar ratio of the cobalt source to the alkyl-substituted imidazole is 1: (2-20); preferably 1: (5-15); more preferably 1: 8.
further, in the above method for preparing a cobalt sulfide/carbon composite positive electrode material, the mass ratio of the cobalt-containing organic metal framework material to the sulfur source is 1: (0.5-2); preferably (0.8-1.2); more preferably 1: 1.
Further, in the preparation method of the cobalt sulfide/carbon composite cathode material, the first preset temperature is 120-200 ℃; preferably 150 ℃ and 180 ℃; the holding time at the first preset temperature is 5-20 h, preferably 8-15 h.
Further, in the preparation method of the cobalt sulfide/carbon composite cathode material, the second preset temperature is 200-900 ℃; preferably 250-500 ℃; the heat treatment time at the second preset temperature is 1-6 h, preferably 2-4.5 h.
According to the preparation method of the cobalt sulfide/carbon composite cathode material provided by the first aspect of the invention, a cobalt source and alkyl substituted imidazole react in an aqueous solution to prepare a cobalt-containing organic metal framework material with a sheet structure; in the cobalt-containing organic metal framework material, cobalt and ligand organic molecules are uniformly distributed in a three-dimensional framework, and a structure in which cobalt sulfide is uniformly dispersed in a carbon framework can be formed in situ through sulfurization treatment of the cobalt-containing organic metal framework material and a sulfur source, namely, the carbon-coated cobalt sulfide/carbon composite anode material is formed.
In a second aspect, the present invention provides an aluminum-ion battery positive electrode comprising: a cobalt sulfide/carbon composite positive electrode material; the cobalt sulfide/carbon composite cathode material is prepared by the preparation method.
In a third aspect, the present invention provides an aluminum-ion battery comprising: the positive electrode is the positive electrode of the aluminum ion battery.
Drawings
FIG. 1 is a flow chart of a method for preparing a cobalt sulfide/carbon composite positive electrode material according to an embodiment of the present invention;
fig. 2 is an XRD pattern of the cobalt sulfide/carbon composite positive electrode material in example 1 of the present invention;
fig. 3 is an SEM image of the cobalt sulfide/carbon composite cathode material prepared in example 1 of the present invention;
fig. 4 is a first charge-discharge curve of an aluminum ion battery assembled using the cobalt sulfide/carbon composite positive electrode material in example 1 of the present invention;
fig. 5 is a discharge cycle diagram of an aluminum ion battery assembled using a cobalt sulfide/carbon composite cathode material prepared in example 1 of the present invention;
fig. 6 is a graph showing the discharge cycle of an aluminum ion battery of comparative example 1 of the present invention assembled using commercially available cobalt sulfide.
Detailed Description
While the preferred embodiments of the present invention are described below, it should be understood that various changes and modifications can be made by one skilled in the art without departing from the principles of the invention, and such changes and modifications are also considered to be within the scope of the invention.
Referring to fig. 1, a first aspect of the present invention provides a method for preparing a cobalt sulfide/carbon composite cathode material, including the following steps:
and step S1, respectively dissolving a cobalt source and alkyl substituted imidazole in a solvent according to a preset proportion to form solutions, then mixing the two solutions, standing for settling, centrifuging, washing and drying to obtain the cobalt-containing organic metal framework material.
Specifically, the cobalt source may be at least one of cobalt nitrate, cobalt sulfate, and cobalt chloride. The alkyl substituted imidazole can be at least one of 2-methylimidazole, 2-ethylimidazole and 1, 2-dimethylimidazole; 2-methylimidazole is preferred. Wherein the molar ratio of the cobalt source to the alkyl substituted imidazole is 1: (2-20); preferably 1: (5-15); more preferably 1: 8. for example, the molar ratio of cobalt source to alkyl substituted imidazole may be 1: 2. 1: 3. 1: 4. 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10, 1:15, 1:20, etc.
The solvent may include one or more of methanol, ethanol and water, preferably one of them, and further preferably water, thereby further facilitating the obtaining of the cobalt-containing organic metal framework material in a sheet form.
In this step, the centrifugation rate of the settled mixed solution during centrifugation may be selected according to actual conditions, and this embodiment does not limit the rate at all. When the product after centrifugation is washed, a water washing mode can be selected; and drying the product after washing at a certain temperature or naturally drying at normal temperature.
In the step, the obtained flaky cobalt-containing organic metal framework material can expose more active components, and is favorable for improving the utilization rate of the active material and further favorable for improving the capacitance of the material.
And step S2, keeping the temperature of the cobalt-containing organic metal framework material and the sulfur source at a first preset temperature for a period of time, cooling to room temperature, centrifuging, washing and drying to obtain the carbon-coated cobalt sulfide composite material.
Specifically, the sulfur source is at least one of thioacetamide, thiourea and sublimed sulfur. Wherein the mass ratio of the cobalt-containing organic metal framework material to the sulfur source is 1: (0.5-2); preferably 1: (0.8-1.2); further preferably 1: 1. In order to achieve sufficient sulfidation of the material, the molar ratio of the sulfur source to the cobalt source should be suitably excessive.
When the method is specifically implemented, the sheet cobalt-containing organic metal framework material is placed into a hydrothermal reaction kettle, a sulfur source is added into the hydrothermal reaction kettle, a kettle cover is screwed, and the temperature is set for reaction. In the reaction, the sulfur source is decomposed to release hydrogen sulfide gas, the hydrogen sulfide gas and cobalt generate cobalt sulfide, meanwhile, the organic ligand in the organic metal framework material is partially carbonized in the hydrothermal process to form a carbon framework, and a structure that the cobalt sulfide is uniformly dispersed in the carbon framework is formed in situ.
In order to ensure that the sheet shape of the cobalt-containing organic metal framework material is well maintained, the first preset temperature is 120-200 ℃; preferably 150 ℃ and 180 ℃; for example, the temperature can be 120 ℃, 150 ℃, 160 ℃, 180 ℃, 200 ℃ and the like; the heat preservation time at the first preset temperature is 5-20 h, preferably 8-15 h; for example, the incubation time may be 5h, 8h, 10 h, 12h, 15h, 20h, or the like.
In the step, a sheet-shaped cobalt-containing organic metal framework material is subjected to hydrothermal reaction under the conditions of preset temperature and time, cobalt can be carbonized into cobalt sulfide while a cobalt ion ligand organic matter is carbonized, and a structure in which the cobalt sulfide is uniformly dispersed in a carbon framework is formed in situ; thus, the carbon material is favorable for better protecting the active cobalt sulfide component and preventing the cobalt sulfide from dissolving out in the charging and discharging processes.
The above obviously shows that, in the preparation method of the cobalt sulfide/carbon composite cathode material provided by the invention, the cobalt source and the alkyl substituted imidazole react in the aqueous solution to prepare the cobalt-containing organic metal framework material with a sheet structure; in the cobalt-containing organic metal framework material, cobalt and ligand organic molecules are uniformly distributed in a three-dimensional framework, and a structure in which cobalt sulfide is uniformly dispersed in a carbon framework can be formed in situ through sulfurization treatment of the cobalt-containing organic metal framework material and a sulfur source, namely, a carbon-coated cobalt sulfide/carbon composite anode material of the cobalt sulfide is formed.
In the embodiment, as the temperature in the hydrothermal reaction process in the step 2 is low (120-200 ℃), the carbonization process of the organic matter is incomplete, so that the prepared composite material has poor crystallinity and low conductivity; therefore, the method may further include a step S3 of heating the cobalt sulfide/carbon composite positive electrode material to a second preset temperature not lower than the first preset temperature under an inert protective atmosphere, performing a heat treatment at the second preset temperature for a period of time, and cooling the cobalt sulfide/carbon composite positive electrode material (i.e., the heating, the heat treatment, and the cooling in the step S3 are performed under an inert protective gas).
In specific implementation, the composite cathode material obtained in step S2 is placed in a tube furnace, and after inert shielding gas is introduced into the heating furnace for heating and heat treatment, the composite cathode material can be naturally cooled. Wherein, the inert shielding gas can be one or more of nitrogen, argon, helium and neon. The second preset temperature is 200-900 ℃; preferably 250-500 ℃; for example, the second predetermined temperature may be 200 ℃, 250 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 780 ℃, 800 ℃, 900 ℃ or the like; the heat treatment time at the second preset temperature is 1-6 h, preferably 2-4.5h, for example, the heat treatment time is 1h, 2h, 3h, 4.5h, 6 h.
In the step, the carbon-coated cobalt sulfide composite material can be further carbonized through high-temperature treatment, so that the crystallinity of the cobalt sulfide is improved, the conductivity of the cobalt sulfide is further improved, and the capacity is favorably exerted; meanwhile, the high-temperature treatment can ensure that the flaky shape of the cobalt-containing machine metal frame material is not changed, namely the utilization rate of the active material is ensured.
The invention provides an aluminum ion battery anode in a second aspect, which comprises a cobalt sulfide/carbon composite anode material; the cobalt sulfide/carbon composite anode material is prepared by the preparation method.
Specifically, the obtained cobalt sulfide/carbon composite electrode material is used as a positive electrode active material, sodium carboxymethylcellulose (CMC) is used as a binder, and conductive carbon black (Super P) is used as a conductive agent, and the cobalt sulfide/carbon composite electrode material and the conductive carbon black are mixed according to a mass ratio of 80:10:10 to prepare the positive electrode of the aluminum ion battery.
The third aspect of the invention provides an aluminum ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is the positive electrode of the aluminum ion battery.
Specifically, the negative electrode, the separator, and the electrolyte may be conventional choices in the art, and this embodiment does not limit them. In this example, the aluminum ion battery anode prepared in the above example was used as the anode, the aluminum sheet was used as the cathode, the glass fiber was used as the separator, and AlCl was used as the separator3The/1-ethyl-3-methylimidazole hydrochloride ionic liquid is used as electrolyte and assembled into a battery according to the existing assembly mode.
The method for preparing the cobalt sulfide/carbon composite positive electrode material, the positive electrode for an aluminum ion battery, and the aluminum ion battery according to the present invention will be described below with reference to specific examples.
Example 1
Respectively dissolving 0.58g of cobalt nitrate hexahydrate and 1.31g of 2-methylimidazole in 40 mL of water, mixing the two solutions, standing for settling, centrifuging, washing with water and drying to obtain an organic metal framework material containing cobalt;
dispersing 50mg of the cobalt-containing organic metal framework material and 50mg of thioacetamide in 80mL of water, pouring the mixture into a hydrothermal reaction kettle, preserving the heat for 20 hours at 120 ℃, cooling to room temperature, centrifuging, washing with water, and drying at 80 ℃ to obtain a cobalt sulfide/carbon composite cathode material;
and under the argon atmosphere, heating the cobalt sulfide/carbon composite anode material to 300 ℃ in a tube furnace, carrying out heat treatment for 1h, and cooling the cobalt sulfide/carbon composite anode material to obtain the cobalt sulfide/carbon composite anode material with better conductivity.
Example 2
Respectively dissolving 0.58g of cobalt sulfate hexahydrate and 0.66 g of 2-methylimidazole in 40 mL of water, mixing the two solutions, standing for settling, centrifuging, washing with water and drying to obtain an organic metal framework material containing cobalt;
dispersing 50mg of the cobalt-containing organic metal framework material and 50mg of thioacetamide in 80mL of water, pouring the mixture into a hydrothermal reaction kettle, preserving the heat for 5 hours at 180 ℃, cooling to room temperature, centrifuging, washing with water, and drying at 70 ℃ to obtain a cobalt sulfide/carbon composite cathode material;
and under the nitrogen atmosphere, heating the cobalt sulfide/carbon composite anode material to 500 ℃ in a tubular furnace, carrying out heat treatment for 6 hours, and cooling the cobalt sulfide/carbon composite anode material to obtain the cobalt sulfide/carbon composite anode material with better conductivity.
Example 3
Respectively dissolving 0.58g of cobalt chloride hexahydrate and 1.31g of 2-methylimidazole in 40 mL of water, mixing the two solutions, standing for settling, centrifuging, washing with water and drying to obtain an organic metal framework material containing cobalt;
dispersing 50mg of the cobalt-containing organic metal framework material and 40 mg of sublimed sulfur in 80mL of water, pouring the mixture into a hydrothermal reaction kettle, preserving the heat for 15h at 150 ℃, cooling to room temperature, centrifuging, washing with water, and drying at 60 ℃ to obtain a cobalt sulfide/carbon composite cathode material;
and under the argon atmosphere, heating the cobalt sulfide/carbon composite anode material to 250 ℃ in a tube furnace, carrying out heat treatment for 2 hours, and cooling the cobalt sulfide/carbon composite anode material to obtain the cobalt sulfide/carbon composite anode material with better conductivity.
Example 4
Respectively dissolving 0.58g of cobalt nitrate hexahydrate and 1.1 g of 2-methylimidazole in 40 mL of water, mixing the two solutions, standing for settling, centrifuging, washing with water and drying to obtain an organic metal framework material containing cobalt;
dispersing 50mg of the cobalt-containing organic metal framework material and 50mg of thioacetamide in 80mL of water, pouring the mixture into a hydrothermal reaction kettle, preserving the heat for 12h at 200 ℃, cooling to room temperature, centrifuging, washing with water, and drying at 80 ℃ to obtain a cobalt sulfide/carbon composite cathode material;
and under the nitrogen atmosphere, heating the cobalt sulfide/carbon composite anode material to 780 ℃ in a tubular furnace, carrying out heat treatment for 3 hours, and cooling the cobalt sulfide/carbon composite anode material to obtain the cobalt sulfide/carbon composite anode material with better conductivity.
Example 5
Respectively dissolving 0.58g of cobalt nitrate hexahydrate and 1.2 g of 2-methylimidazole in 40 mL of water, mixing the two solutions, standing for settling, centrifuging, washing with water and drying to obtain an organic metal framework material containing cobalt;
dispersing 50mg of the cobalt-containing organic metal framework material and 50mg of thiourea in 80mL of water, pouring the mixture into a hydrothermal reaction kettle, preserving the heat for 8 hours at the temperature of 150 ℃, cooling to room temperature, centrifuging, washing with water, and drying at the temperature of 80 ℃ to obtain a cobalt sulfide/carbon composite cathode material;
and under the argon atmosphere, heating the cobalt sulfide/carbon composite anode material to 900 ℃ in a tube furnace, carrying out heat treatment for 1h, and cooling the cobalt sulfide/carbon composite anode material to obtain the cobalt sulfide/carbon composite anode material with better conductivity.
Comparative example 1
And selecting commercially available cobalt sulfide without a carbon coating structure as the anode of the aluminum ion battery to assemble the aluminum ion battery.
Scanning electron microscope test and XRD test are respectively carried out on the surface of the cobalt sulfide/carbon composite anode material subjected to heat treatment in the embodiment 1, and the results are shown in figures 2-3, and as can be seen from figure 2, the crystal form of the cobalt sulfide/carbon composite anode material subjected to heat treatment in the invention is consistent with that of a standard card JCPDS (JCPDS) 65-3322. As can be seen from FIG. 3, the composite material is of a nano-sheet structure, has a large area-thickness ratio, can expose more active surfaces, shortens an ion transmission path, and is beneficial to the exertion of capacity. The flaky material is assembled by cobalt sulfide nanosheets and carbon coated on the surfaces of the cobalt sulfide nanosheets, the cobalt sulfide and the high-conductivity carbon material are uniformly distributed, the overall conductivity of the positive electrode material is improved, the structural integrity of the material in the circulating process can be kept due to the carbon-coated structure, the loss of active substances is prevented, the high capacitance is kept, and the capacity attenuation rate of the aluminum ion battery in the circulating process is reduced.
The heat-treated cobalt sulfide/carbon composite positive electrode material prepared in example 1 is used as a positive electrode active material, sodium carboxymethylcellulose (CMC) is used as a binder, conductive carbon black (Super P) is used as a conductive agent, a positive electrode is prepared according to a mass ratio of 80:10:10, a high-purity aluminum sheet is used as a negative electrode, glass fiber is used as a diaphragm, AlCl is used as a diaphragm3The 1-ethyl-3-methylimidazole hydrochloride ionic liquid is used as electrolyte to assemble a battery; electrochemical performance tests were performed on the assembled batteries, respectively, and the results are shown in fig. 4 to 5. As can be seen from fig. 4-5, the first discharge capacity of the aluminum ion battery assembled by the cobalt sulfide/carbon composite cathode material after heat treatment in example 1 of the present invention reaches 434mAh/g, and after 50 cycles, the capacity is 114 mAh/g; as can be seen from fig. 6, the first capacity of the aluminum ion battery assembled using commercial cobalt sulfide was 272 mAh/g, and the capacity after 50 cycles was only 10mAh/g, while fig. 6 is a discharge cycle chart of the aluminum ion battery in comparative example 1.
From the results of example 1 and comparative example 1, it is known that the cobalt sulfide/carbon composite material having a nano-sheet structure can effectively improve the cycle stability of the sulfur-based positive electrode material, and the carbonization degree and crystallinity of the material can be improved by performing the carbonization treatment, thereby improving the conductivity of the material and contributing to the capacity.
In summary, according to the preparation method of the cobalt sulfide/carbon composite cathode material provided by the invention, a cobalt source and alkyl substituted imidazole react in an aqueous solution to prepare a cobalt-containing organic metal framework material with a sheet structure; because cobalt ions in the cobalt-containing organic metal framework material are uniformly dispersed, cobalt sulfide can be better distributed in a carbon framework after vulcanization treatment, active substances can be effectively prevented from dissolving out, the capacity of the battery is prevented from being greatly attenuated in the charging and discharging processes, the cyclic charging and discharging capacity of the aluminum ion battery is favorably improved, and the cyclic retention rate of the aluminum ion battery is better; the preparation method of the cobalt sulfide/carbon composite cathode material is applied to the preparation of the aluminum ion battery, and has good industrial application prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The preparation method of the cobalt sulfide/carbon composite cathode material is characterized by comprising the following steps of:
step 1, respectively dissolving a cobalt source and alkyl substituted imidazole in a solvent according to a preset proportion to form a solution, then mixing the two solutions, standing and settling, and processing to obtain a cobalt-containing organic metal framework material;
and 2, preserving the temperature of the cobalt-containing organic metal framework material and a sulfur source at a first preset temperature for a period of time, cooling to room temperature, and treating to obtain the cobalt sulfide/carbon composite anode material.
2. The method for preparing a cobalt sulfide/carbon composite positive electrode material according to claim 1, further comprising a step 3 of heating the cobalt sulfide/carbon composite positive electrode material to a second preset temperature not lower than the first preset temperature in an inert protective atmosphere, performing heat treatment at the second preset temperature for a period of time, and then cooling the cobalt sulfide/carbon composite positive electrode material.
3. The method for preparing a cobalt sulfide/carbon composite cathode material according to claim 2, wherein the inert shielding gas is one or more of nitrogen, argon, helium and neon, and the solvent is one or more of methanol, ethanol and water.
4. The method for preparing a cobalt sulfide/carbon composite positive electrode material according to claim 1, wherein the cobalt source is at least one of cobalt nitrate, cobalt sulfate, and cobalt chloride; and/or the alkyl substituted imidazole is at least one of 2-methylimidazole, 2-ethylimidazole and 1, 2-dimethylimidazole; and/or the sulfur source is at least one of thioacetamide, thiourea and sublimed sulfur.
5. The method for producing a cobalt sulfide/carbon composite positive electrode material according to any one of claims 1 to 4, wherein the molar ratio of the cobalt source to the alkyl-substituted imidazole is 1: (2-20); preferably 1: (5-15); more preferably 1: 8.
6. the method for preparing a cobalt sulfide/carbon composite cathode material according to any one of claims 1 to 4, wherein the mass ratio of the cobalt-containing organic metal framework material to the sulfur source is 1 (0.5-2), preferably (0.8-1.2); more preferably 1: 1.
7. The method for preparing the cobalt sulfide/carbon composite cathode material as claimed in any one of claims 1 to 4, wherein the first predetermined temperature is 120-200 ℃; preferably 150 ℃ and 180 ℃; the holding time at the first preset temperature is 5-20 h, preferably 8-15 h.
8. The method for preparing the cobalt sulfide/carbon composite cathode material as claimed in claim 2, wherein the second predetermined temperature is 200-900 ℃; preferably 250-500 ℃; the heat treatment time at the second preset temperature is 1-6 h, preferably 2-4.5 h.
9. An aluminum-ion battery positive electrode comprising: a cobalt sulfide/carbon composite positive electrode material; the cobalt sulfide/carbon composite positive electrode material is prepared by the preparation method according to any one of claims 1 to 8.
10. An aluminum-ion battery, comprising: a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the positive electrode is the aluminum-ion battery positive electrode according to claim 9.
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