CN113130905A - Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof - Google Patents
Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof Download PDFInfo
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- CN113130905A CN113130905A CN202110408426.0A CN202110408426A CN113130905A CN 113130905 A CN113130905 A CN 113130905A CN 202110408426 A CN202110408426 A CN 202110408426A CN 113130905 A CN113130905 A CN 113130905A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000004744 fabric Substances 0.000 title claims abstract description 61
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000002135 nanosheet Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 18
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- VJGRFWVLROCEGS-UHFFFAOYSA-N cobalt;tetrahydrate Chemical compound O.O.O.O.[Co].[Co].[Co] VJGRFWVLROCEGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 150000004685 tetrahydrates Chemical class 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 discloses a preparation method of an ultra-small cobalt sulfide nanosheet/carbon cloth composite material, which comprises the following steps of (1) (0.7-1.1) weighing analytically pure cobalt acetate, tetrahydrate and sulfur powder according to the mass ratio, adding the cobalt acetate, the tetrahydrate and the sulfur powder into an ethanol solution, and stirring to obtain a solution A with the cobalt acetate concentration of 0.15-0.2 mol/L; standing the solution A, performing suction filtration to collect powder, cleaning and drying to obtain powder A; cutting the carbon cloth into small pieces, completely soaking the small pieces in a concentrated nitric acid solution, reacting for 2-4h in an oven at 90 ℃, cooling and then cleaning to obtain the pretreated carbon cloth; step four, respectively placing the pretreated carbon cloth and the powder A at two ends of the magnetic field, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture to 800 ℃ in the protection of argon atmosphere, keeping the temperature for 1 to 3 hours at the heating rate of 3 to 7 ℃/min, and taking out a sample after cooling to room temperature to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material; the invention effectively improves the electrochemical activity and rate capability of the cobalt sulfide electrode material.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, relates to a sodium ion battery cathode material and a preparation method thereof, and particularly relates to an ultra-small cobalt sulfide nanosheet/carbon cloth composite material and a preparation method thereof.
Technical Field
With the popularization of portable electronic products and the rapid development of electric automobiles, the requirements on energy storage technology are higher and higher. The carbon-based material is a host material widely used in secondary batteries, such as carbon nanotubes, porous carbon, graphene nanoribbons, carbon fibers, and the like. Cobalt sulfide belongs to transition metal sulfide, belongs to a conversion reaction type cathode material in a secondary battery, but has poor cycle performance due to large volume expansion, and causes electrode pulverization; slower kinetics lead to poorer rate performance. Carbon cloth is widely used as a substrate of a flexible electrode material due to its good mechanical strength, electrical conductivity and flexibility. In recent years, many researchers have used flexible electrode materials by growing active materials such as metal oxides, metal sulfides, etc. on carbon cloth. The flexible electrode material does not need to add a binder and a conductive agent in the preparation process, so that the preparation steps are reduced, and the quality and the cost of the electrode material are reduced. In addition, the carbon cloth can effectively relieve the volume change of the active material in the charging and discharging process, thereby improving the performance of the active material. Therefore, the research on the flexible electrode material taking the carbon cloth as the substrate has important significance for the development of flexible energy storage devices.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an ultra-small cobalt sulfide nanosheet/carbon cloth composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an ultra-small cobalt sulfide nanosheet/carbon cloth composite material comprises the following steps:
weighing analytically pure cobalt acetate, tetrahydrate and sulfur powder according to the mass ratio of 1 (0.7-1.1), adding the cobalt acetate, the tetrahydrate and the sulfur powder into an ethanol solution, and stirring to obtain a solution A with the cobalt acetate concentration of 0.15-0.2 mol/L;
standing the solution A, performing suction filtration to collect powder, cleaning and drying to obtain powder A;
cutting the carbon cloth into small pieces, completely soaking the small pieces in a concentrated nitric acid solution, reacting for 2-4h in an oven at 90 ℃, cooling and then cleaning to obtain the pretreated carbon cloth;
and step four, respectively placing the pretreated carbon cloth and the powder A at two ends of the magnetic field, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture in the protection of argon atmosphere to 800 ℃, keeping the temperature at the rate of 3-7 ℃/min for 1-3h, and taking out a sample after cooling to room temperature to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
The invention also has the following technical characteristics:
preferably, the standing method in the second step is standing for 4-7 hours at normal temperature in a dark place.
Preferably, the cleaning method in the second step is to repeatedly and alternately clean the substrate with deionized water and absolute ethyl alcohol for 3-5 times.
Preferably, the drying method in the second step is drying for 5-10h at 70 ℃ in a vacuum drying oven.
Preferably, the carbon cloth is cut into small pieces with the size of 2cm by 3cm in the third step.
Preferably, the cleaning method in the third step is to repeatedly and alternately clean the substrate for 3 to 5 times by using deionized water and absolute ethyl alcohol.
The invention also provides the ultra-small cobalt sulfide nanosheet/carbon cloth composite material prepared by the preparation method of the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the carbon cloth is added to be compounded with the cobalt sulfide, and a conductive network formed by carbon fibers in the conductive carbon cloth is beneficial to the diffusion of electrolyte and can improve the conductivity of the cobalt sulfide; meanwhile, the carbon cloth as a self-supporting body can avoid adding a conductive agent and a binder in the preparation process of the electrode, simplify the process flow, improve the capacity contribution of the cobalt sulfide, and further improve the electrochemical activity and the rate capability of the electrode material;
the cobalt sulfide particle size is in the nanometer size range, and the composite material can remarkably improve the integrity of a microstructure, is beneficial to ion transmission and electron transfer and improves the electrochemical performance of the composite material due to the advantage of a nanometer structure;
the raw materials used in the invention are common materials, are cheap and easy to obtain, have low cost, do not need post treatment, are environment-friendly, have simple process and easy operation, and can be suitable for large-scale production.
Drawings
FIG. 1 is an XRD diffractogram of the product obtained in example 1 of the present invention
FIG. 2 is an SEM topography of the product obtained in example 1 of the invention
FIG. 3 is a graph showing the cycle performance of the product obtained in example 1 of the present invention
Detailed Description
Example 1:
1) a certain amount of analytically pure cobalt acetate, tetrahydrate and sulfur powder are added into an ethanol solution together, and a clear solution A is obtained by stirring. The concentration of the cobalt acetate is 0.15mol/L, and the mass ratio of the cobalt acetate to the sulfur powder is 1: 0.7;
2) standing the clear solution A at normal temperature in a dark place for 4h, performing suction filtration, collecting powder, repeatedly and alternately cleaning with deionized water and absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 70 ℃ for 5h to obtain powder A;
3) cutting the carbon cloth into 2cm by 3cm, completely soaking the carbon cloth in a concentrated nitric acid solution, reacting for 2 hours in an oven at 90 ℃, and repeatedly and alternately cleaning for 3-5 times by using deionized water and absolute ethyl alcohol after cooling to obtain pretreated carbon cloth;
4) placing the pretreated carbon cloth and the powder A at two ends of the magnetic field respectively, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture to 700 ℃ under the protection of argon atmosphere, raising the temperature at a rate of 7 ℃/min, and preserving the heat for 1 h. And after the temperature is reduced to the room temperature, taking out the sample to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
Example 2:
1) a certain amount of analytically pure cobalt acetate, tetrahydrate and sulfur powder are added into an ethanol solution together, and a clear solution A is obtained by stirring. The concentration of the cobalt acetate is 0.18mol/L, and the mass ratio of the cobalt acetate to the sulfur powder is 1: 0.9;
2) standing the clear solution A at normal temperature in a dark place for 5h, performing suction filtration, collecting powder, repeatedly and alternately cleaning with deionized water and absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 70 ℃ for 8h to obtain powder A;
3) cutting the carbon cloth into 2cm by 3cm, completely soaking the carbon cloth in a concentrated nitric acid solution, reacting for 3h in an oven at 90 ℃, and repeatedly and alternately cleaning for 3-5 times by using deionized water and absolute ethyl alcohol after cooling to obtain pretreated carbon cloth;
4) placing the pretreated carbon cloth and the powder A at two ends of the magnetic field respectively, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture to 750 ℃ under the protection of argon atmosphere, raising the temperature at a rate of 5 ℃/min, and preserving the heat for 2 hours. And after the temperature is reduced to the room temperature, taking out the sample to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
Example 3:
1) a certain amount of analytically pure cobalt acetate, tetrahydrate and sulfur powder are added into an ethanol solution together, and a clear solution A is obtained by stirring. The concentration of the cobalt acetate is 0.2mol/L, and the mass ratio of the cobalt acetate to the sulfur powder is 1: 1.1;
2) standing the clear solution A at normal temperature in a dark place for 7h, performing suction filtration, collecting powder, repeatedly and alternately cleaning with deionized water and absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain powder A;
3) cutting the carbon cloth into 2cm by 3cm, completely soaking the carbon cloth in a concentrated nitric acid solution, reacting for 4 hours in an oven at 90 ℃, and repeatedly and alternately cleaning for 3-5 times by using deionized water and absolute ethyl alcohol after cooling to obtain pretreated carbon cloth;
4) placing the pretreated carbon cloth and the powder A at two ends of the magnetic field respectively, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture to 800 ℃ under the protection of argon atmosphere, heating at a rate of 3 ℃/min, and preserving the heat for 3 hours. And after the temperature is reduced to the room temperature, taking out the sample to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
FIG. 1 is an XRD of the product obtained in example 1, and it can be seen that the product phase is comparable to standard card PDF #03-0631Co9S8Correspondingly, the peak of the steamed bun is brought by the carbon cloth, and the successful preparation of the cobalt sulfide/carbon cloth composite material is proved.
FIG. 2 is an SEM image analysis of the product obtained in example 1, and it can be seen from the low-power graph a that the composite material has a uniform appearance and cobalt sulfide is uniformly distributed on the surface of the carbon cloth; from the high power graph b, it can be seen that the cobalt sulfide flakes are in the nanometer scale and are staggered with each other.
FIG. 3 is an electrochemical performance test analysis of the product obtained in example 1, the capacity of the cell was maintained at 650mAh/g for 60 cycles at a current density of 1A/g in the voltage range of 0.3-3V, and the slight performance decay was probably due to the activation process, and the overall cycle stability was good.
Claims (7)
1. A preparation method of an ultra-small cobalt sulfide nanosheet/carbon cloth composite material is characterized by comprising the following steps:
weighing analytically pure cobalt acetate, tetrahydrate and sulfur powder according to the mass ratio of 1 (0.7-1.1), adding the cobalt acetate, the tetrahydrate and the sulfur powder into an ethanol solution, and stirring to obtain a solution A with the cobalt acetate concentration of 0.15-0.2 mol/L;
standing the solution A, performing suction filtration to collect powder, cleaning and drying to obtain powder A;
cutting the carbon cloth into small pieces, completely soaking the small pieces in a concentrated nitric acid solution, reacting for 2-4h in an oven at 90 ℃, cooling and then cleaning to obtain the pretreated carbon cloth;
and step four, respectively placing the pretreated carbon cloth and the powder A at two ends of the magnetic field, placing the pretreated carbon cloth and the powder A into a tubular furnace together, calcining the mixture to 800 ℃ in the protection of argon atmosphere, keeping the temperature rising rate at 3-7 ℃/min, keeping the temperature for 1-3h in a sealed manner, and taking out a sample after the temperature is reduced to room temperature to obtain the ultra-small cobalt sulfide nanosheet/carbon cloth composite material.
2. The method for preparing an ultra-small cobalt sulfide nanosheet/carbon cloth composite material of claim 1, wherein the standing method in step two is standing at normal temperature in a dark place for 4-7 h.
3. The method for preparing ultra-small cobalt sulfide nanosheet/carbon cloth composite material of claim 2, wherein the cleaning in step two is repeated and alternate cleaning with deionized water and absolute ethanol for 3-5 times.
4. The method for preparing ultra-small cobalt sulfide nanosheet/carbon cloth composite material of claim 3, wherein the drying method in step two is drying at 70 ℃ for 5-10h in a vacuum drying oven.
5. A method for preparing ultra-small cobalt sulfide nanosheet/carbon cloth composite material as recited in claim 1 in which the carbon cloth is cut into pieces of 2cm by 3cm in size in step three.
6. The method for preparing ultra-small cobalt sulfide nanosheet/carbon cloth composite material of claim 5, wherein the cleaning in step three is repeated and alternate cleaning with deionized water and absolute ethyl alcohol for 3-5 times.
7. An ultra-small cobalt sulfide nanosheet/carbon cloth composite prepared using the method of preparing an ultra-small cobalt sulfide nanosheet/carbon cloth composite of claims 1-6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114703505A (en) * | 2022-04-04 | 2022-07-05 | 昆明理工大学 | Preparation method of metal atom electrocatalyst with stable carbon atom coordination |
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