CN110600275A - Bowl-shaped metal sulfide/carbon composite electrode material and preparation method and application thereof - Google Patents

Bowl-shaped metal sulfide/carbon composite electrode material and preparation method and application thereof Download PDF

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Publication number
CN110600275A
CN110600275A CN201910889219.4A CN201910889219A CN110600275A CN 110600275 A CN110600275 A CN 110600275A CN 201910889219 A CN201910889219 A CN 201910889219A CN 110600275 A CN110600275 A CN 110600275A
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electrode material
composite electrode
carbon composite
metal sulfide
carbon
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CN110600275B (en
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赵悦
张海燕
李宽
程奥
林迎曦
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Guangdong University of Technology
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 belongs to the technical field of energy storage materials, and particularly relates to a bowl-shaped metal sulfide/carbon composite electrode material as well as a preparation method and application thereof. The invention provides a metal sulfide/carbon composite electrode material, which is of a bowl-shaped structure; the metal sulfide/carbon composite electrode material includes carbon and a metal sulfide doped in the carbon. The metal sulfide/carbon composite electrode material is of a bowl-shaped structure, the specific surface area is large, the metal sulfide and the carbon material are compounded, the specific capacity and the power density of the carbon material can be increased by the metal sulfide, the conductivity and the cycling stability of the metal sulfide can be improved by the carbon material, and experimental results show that the metal sulfide/carbon composite electrode material is high in specific capacity and has good stability and rate capability.

Description

Bowl-shaped metal sulfide/carbon composite electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a bowl-shaped metal sulfide/carbon composite electrode material as well as a preparation method and application thereof.
Background
At present, the rapid development of energy storage technology is promoted by the emergence of energy crisis, new energy is urgently developed and utilized, wind energy, solar energy and the like are widely researched, but the wind energy, the solar energy and the like are limited by factors such as weather, climate, geographical position and the like, have intermittency and have certain limitation in practical application. Supercapacitors are considered ideal candidates for energy storage devices due to their fast charge and discharge, long cycle life, and excellent power density. Among these, the overall performance of supercapacitors and electrochemical storage devices depends mainly on the most important component, i.e. the electrode material. The structural design of the electrode material and the performance of the material itself are the key factors in determining the quality of the electrode material.
Therefore, the search for an electrode material having good conductivity and high specific capacity has been a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a bowl-shaped metal sulfide/carbon composite electrode material, and a preparation method and an application thereof.
The specific technical scheme of the invention is as follows:
a metal sulfide/carbon composite electrode material is of a bowl-shaped structure;
the metal sulfide/carbon composite electrode material includes carbon and a metal sulfide doped in the carbon.
Preferably, the metal in the metal sulfide is a transition metal;
the transition metal is selected from one or more of cobalt, nickel, manganese, tin and molybdenum.
Preferably, the mass ratio of the metal sulfide to the carbon is 1: (4-10).
Preferably, the diameter of the bowl opening of the bowl-shaped structure is 170 nm-200 nm.
The invention also provides a preparation method of the metal sulfide/carbon composite electrode material, which comprises the following steps:
a) adding microspheres, metal salt and organic resin into a solvent, and stirring and ultrasonically treating to obtain a first product;
b) drying the first product, and carbonizing in an inert atmosphere and/or a nitrogen atmosphere to obtain a second product;
c) etching the second product, and drying to obtain a third product;
d) and carrying out a vulcanization reaction on the third product and the sublimed sulfur in an inert atmosphere and/or a nitrogen atmosphere to obtain the bowl-shaped metal sulfide/carbon composite electrode material.
Preferably, the microsphere is SiO2Microspheres or polystyrene microspheres;
the metal salt is selected from one or more of cobalt salt, nickel salt, manganese salt, tin salt and molybdenum salt;
the organic resin is selected from one or more of PVDF, PAA and PVA.
Preferably, the microsphere is SiO2The metal salt is cobalt acetate, and the organic resin is PVDF;
the mass ratio of the microspheres to the metal salt to the organic resin is 1: (1-3): (1-3).
Preferably, the temperature rise rate of the carbonization in the step b) is 2-10 ℃/min;
the carbonization heat preservation temperature is 500-800 ℃;
the carbonization heat preservation time is 2-3 h.
Preferably, the mass ratio of the third product of step d) to the sublimed sulfur is 1: (10-40);
the temperature rise rate of the vulcanization reaction is 2-5 ℃/min;
the heat preservation temperature of the vulcanization reaction is 300-500 ℃;
the heat preservation time of the vulcanization reaction is 3-6 h.
The invention also provides the application of the metal sulfide/carbon composite electrode material prepared by the preparation method in the technical scheme and/or the application of the metal sulfide/carbon composite electrode material prepared by the preparation method in the field of energy storage.
In summary, the invention provides a metal sulfide/carbon composite electrode material, which is a bowl-shaped structure; the metal sulfide/carbon composite electrode material includes carbon and a metal sulfide doped in the carbon. The metal sulfide/carbon composite electrode material is of a bowl-shaped structure, the specific surface area is large, the metal sulfide and the carbon material are compounded, the specific capacity and the power density of the carbon material can be increased by the metal sulfide, the conductivity and the cycling stability of the metal sulfide can be improved by the carbon material, and experimental results show that the metal sulfide/carbon composite electrode material is high in specific capacity and has good stability and rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a diagram of SiO in example 1 of the present invention2Scanning Electron Microscope (SEM) images of the microspheres;
FIG. 2 shows the cobalt oxide/carbon coated SiO prepared after carbonization in example 1 of the present invention2SEM images of microspheres;
fig. 3 is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in example 1 of the present invention;
fig. 4 is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in example 2 of the present invention;
FIG. 5 is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in example 5 of the present invention;
fig. 6 is an XRD spectrum of the cobalt disulfide/carbon composite electrode material prepared in examples 1 and 2 of the present invention;
FIG. 7 is a cyclic voltammogram of the cobalt disulfide/carbon composite electrode material prepared in example 1 of the present invention;
fig. 8 is a constant current charge-discharge curve diagram of the cobalt disulfide/carbon composite electrode material prepared in the embodiment 1 of the present invention.
Detailed Description
The invention provides a bowl-shaped metal sulfide/carbon composite electrode material, and a preparation method and application thereof.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
A metal sulfide/carbon composite electrode material is characterized in that the metal sulfide/carbon composite electrode material is of a bowl-shaped structure;
the metal sulfide/carbon composite electrode material includes carbon and a metal sulfide doped in the carbon.
In the embodiment of the invention, the metal sulfide/carbon composite electrode material is of a bowl-shaped structure, the specific surface area is large, the metal sulfide and the carbon material are compounded, the specific capacity and the power density of the carbon material can be increased by the metal sulfide, the conductivity and the cycling stability of the metal sulfide can be improved by the carbon material, and the experimental result shows that the metal sulfide/carbon composite electrode material has high specific capacity and good stability and rate capability.
In the embodiment of the invention, the metal in the metal sulfide is transition metal;
the transition metal is selected from one or more of cobalt, nickel, manganese, tin and molybdenum.
In the embodiment of the invention, the mass ratio of the metal sulfide to the carbon is 1: (4-10);
in the embodiment of the invention, the diameter of the bowl opening of the bowl-shaped structure is 170 nm-200 nm.
The invention also provides a preparation method of the metal sulfide/carbon composite electrode material, which comprises the following steps:
a) adding microspheres, metal salt and organic resin into a solvent, and stirring and ultrasonically treating to obtain a first product;
b) drying the first product, and carbonizing in an inert atmosphere and/or a nitrogen atmosphere to obtain a second product;
c) etching the second product, and drying to obtain a third product;
d) and carrying out a vulcanization reaction on the third product and the sublimed sulfur in an inert atmosphere and/or a nitrogen atmosphere to obtain the bowl-shaped metal sulfide/carbon composite electrode material.
In the embodiment of the invention, in the step a), the metal salt can be dissolved in the solvent, the microspheres and the organic resin are added, stirring and ultrasonic treatment are carried out, the stirring time is preferably 0.5 h-1 h, more preferably 1h, the ultrasonic treatment time is preferably 1 h-2 h, more preferably 1h, and the metal salt and the organic resin are uniformly coated on the surfaces of the microspheres by stirring and ultrasonic treatment to obtain the first product.
The solvent is selected from one or more of N-methylpyrrolidone (NMP), water, dimethyl sulfoxide and dimethylformamide, and preferably N-methylpyrrolidone and water.
The carbonization in step b) can be carried out in a tube furnace.
Step c) is preferably dried at 80 ℃ for 12 h.
The vulcanization reaction of step d) can be carried out in a tube furnace.
In the embodiment of the invention, the microspheres are SiO2Microspheres or polystyrene microspheres;
the metal salt is selected from one or more of cobalt salt, nickel salt, manganese salt, tin salt and molybdenum salt, preferably cobalt salt, the cobalt salt is cobalt acetate and/or cobalt chloride, and more preferably cobalt acetate;
the organic resin is selected from one or more of polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and polyvinyl alcohol (PVA).
SiO2The microspheres are prepared by a Stober method, SiO2The size of the microsphere is easy to regulate and specifically comprises:
sequentially adding ethanol, water and ammonia water into a beaker, uniformly stirring the mixture by using a magnetic stirrer at room temperature, slowly dropwise adding Tetraethoxysilane (TEOS) into the uniformly mixed solution under the stirring condition to perform hydrolysis reaction, sealing the opening of the beaker by using a polyethylene film after the dropwise adding is finished, allowing white precipitate to appear in 1-5 min, stirring the mixture to allow the reaction to be finished, performing centrifugal cleaning, and drying to obtain SiO2And (3) microspheres. Wherein the rotating speed of the centrifugation is preferably 5000rpm to 8000rpm, and more preferably 8000 rpm; the drying conditions are preferably 60 ℃ to 80 ℃ for 12 hours to 24 hours, more preferably 80 ℃ for 24 hours.
And c) carrying out initial etching treatment to obtain a complete hollow shell structure, wherein when the interior becomes a hollow shell and is subjected to external pressure, stress can be generated to cause a part of the shell to collapse, and a third product of the bowl-shaped structure is obtained.
The microspheres are SiO2When the microspheres are formed, the second product can be etched in the step c) by NaOH for multiple times of washing. The concentration of NaOH is 2M, and the washing times are preferably 10-20 times.
In the embodiment of the invention, the microspheres are SiO2The microsphere comprises a metal salt, an organic resin and a microsphere, wherein the metal salt is cobalt acetate, and the organic resin is PVDF;
the mass ratio of the microspheres to the metal salt to the organic resin is 1: (1-3): (1-3), more preferably 1: 2: 2.
in the embodiment of the invention, the temperature rise rate of carbonization in the step b) is 2-10 ℃/min, preferably 5 ℃/min;
the carbonization heat preservation temperature is 500-800 ℃, and preferably 500 ℃;
the carbonization heat preservation time is 2h to 3h, preferably 2 h.
In the embodiment of the invention, the mass ratio of the third product in the step d) to the sublimed sulfur is 1: (10-40), preferably 1: 30, of a nitrogen-containing gas;
the temperature rise rate of the vulcanization reaction is 2-5 ℃/min, preferably 2 ℃/min;
the heat preservation temperature of the vulcanization reaction is 300-500 ℃, and the optimal temperature is 350 ℃;
the heat preservation time of the vulcanization reaction is 3 to 6 hours, preferably 4 hours.
The preparation method provided by the embodiment of the invention has wide applicability, different metal sulfide/carbon composite electrode materials can be prepared by adopting different metal salts, and the prepared metal sulfide/carbon composite electrode material has a bowl-shaped structure, the size is adjustable, and the specific surface area is obviously improved; meanwhile, carbon in the metal sulfide/carbon composite electrode material is uniformly compounded with metal sulfide, so that the metal sulfide/carbon composite electrode material has good conductivity and a stable bowl-shaped structure. The preparation method provided by the embodiment of the invention is simple in preparation process, and the prepared metal sulfide/carbon composite electrode material is stable in structure and has a wide application prospect.
The invention also provides the application of the metal sulfide/carbon composite electrode material prepared by the preparation method in the technical scheme and/or the application of the metal sulfide/carbon composite electrode material prepared by the preparation method in the field of energy storage, and more preferably the application in the field of supercapacitors.
The metal sulfide such as cobalt disulfide is the main part for providing specific capacity of the supercapacitor, and the carbon material improves the conductivity and stability of the metal sulfide.
For a further understanding of the invention, reference will now be made in detail to the following examples.
Example 1
In this embodiment, the preparation of the cobalt disulfide/carbon composite electrode material includes the following steps:
1) sequentially adding ethanol, water and ammonia water into a beaker, uniformly stirring the mixture by using a magnetic stirrer at room temperature, slowly dropwise adding TEOS into the uniformly mixed solution under the stirring condition for hydrolysis reaction, sealing the opening of the beaker by using a polyethylene film after dropwise addition, allowing white precipitate to appear in 1-5 min, stirring the mixture until the reaction is finished, centrifugally cleaning the mixture at 8000rpm, pouring out supernatant, and drying the white precipitate at the bottom in an oven at the temperature of 80 DEG CDrying for 24h to obtain SiO2And (3) microspheres. FIG. 1 shows SiO in example 1 of the present invention2SEM image of microspheres, FIG. 1 shows SiO2The microspheres are uniform in size and about 200nm in diameter.
2) 0.1g of SiO2And (3) placing the microspheres in 4mL of NMP, stirring at room temperature for 30min, adding 0.2g of cobalt acetate, stirring for 30min, adding 0.2g of PVDF, stirring for 1h, and performing ultrasonic treatment for 1h to obtain a first product.
3) Drying the first product in a drying oven at 80 ℃ for 24h, then placing the dried product in a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 2h for carbonization, and cooling in the furnace to obtain the cobalt oxide/carbon-coated SiO2Microspheres, i.e. the second product. Referring to FIG. 2, there is shown a cobalt oxide/carbon coated SiO solid prepared by carbonization in example 1 of the present invention2SEM image of the microspheres, FIG. 2 shows that the carbonized oxide and carbon material are uniformly coated on SiO2The surface of the microsphere.
4) The second product was washed 20 times with 2M NaOH to remove SiO2And (4) drying the microspheres in an oven at 80 ℃ for 12 hours to obtain the cobalt oxide/carbon composite material, namely a third product.
5) And (3) heating the third product and sublimed sulfur to 350 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, and preserving the heat for 4 hours to carry out a vulcanization reaction to obtain the cobalt disulfide/carbon composite electrode material. Referring to fig. 3, which is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in embodiment 1 of the present invention, fig. 3 shows that the cobalt disulfide/carbon composite electrode material of this embodiment has a bowl-shaped structure, so that the specific surface area of the cobalt disulfide/carbon composite electrode material is increased, the bowl-shaped structure can be well maintained, the cobalt disulfide can be prevented from falling off or changing phase during the reaction process, the cobalt disulfide is compounded with a carbon material, the cobalt disulfide can increase the specific capacity and power density of the carbon material, and the carbon material can improve the conductivity and the cycle stability of the cobalt disulfide.
In the cobalt disulfide/carbon composite electrode material of this embodiment, the mass ratio of cobalt disulfide to carbon is 1: 6.5, the diameter of the bowl opening of the bowl-shaped structure is 186 nm.
Example 2
In this example, a cobalt disulfide/carbon composite electrode material was prepared, and the difference between this example and example 1 is that: replacing NMP in step 2) with water and PVDF with PAA.
Fig. 4 is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in example 2 of the present invention, and fig. 4 shows that the cobalt disulfide/carbon composite electrode material of this embodiment has a bowl-shaped structure, which increases the specific surface area of the cobalt disulfide/carbon composite electrode material, but the bowl-shaped structure is not stable enough compared to the cobalt disulfide/carbon composite electrode material of example 1.
In the cobalt disulfide/carbon composite electrode material of this embodiment, the mass ratio of cobalt disulfide to carbon is 1: 9.8, the diameter of the bowl mouth of the bowl-shaped structure is 173 nm.
Example 3
In this example, a cobalt disulfide/carbon composite electrode material was prepared, and the difference between this example and example 1 is that: the mass of PVDF in step 2) was 0.1 g.
In the cobalt disulfide/carbon composite electrode material of this embodiment, the mass ratio of cobalt disulfide to carbon is 1: 4.2, the diameter of the bowl opening of the bowl-shaped structure is 195 nm.
Example 4
In this example, a cobalt disulfide/carbon composite electrode material was prepared, and the difference between this example and example 1 is that: the temperature of carbonization in step 3) was 600 ℃.
In the cobalt disulfide/carbon composite electrode material of this embodiment, the mass ratio of cobalt disulfide to carbon is 1: 6.3, the diameter of the bowl mouth of the bowl-shaped structure is 182 nm.
Example 5
In this example, a cobalt disulfide/carbon composite electrode material was prepared, and the difference between this example and example 1 is that: in the step 2), cobalt acetate is replaced by cobalt chloride.
Fig. 5 is an SEM image of the cobalt disulfide/carbon composite electrode material prepared in example 5 of the present invention, and fig. 5 shows that the cobalt disulfide/carbon composite electrode material of this embodiment has a bowl-shaped structure, which increases the specific surface area of the cobalt disulfide/carbon composite electrode material, but the bowl-shaped structure is not stable enough compared to the cobalt disulfide/carbon composite electrode material of example 1.
In the cobalt disulfide/carbon composite electrode material of this embodiment, the mass ratio of cobalt disulfide to carbon is 1: 6.3, the bowl mouth diameter of the bowl-shaped structure is 193 nm.
Example 6
In this example, X-ray diffraction analysis is performed on the cobalt disulfide/carbon composite electrode materials prepared in examples 1 and 2, and as a result, please refer to fig. 6, the results show that the cobalt disulfide/carbon composite electrode materials prepared in examples 1 and 2 both have good crystallinity, the crystal structure of cobalt disulfide is not damaged by the composition of the cobalt disulfide/carbon composite electrode materials with a carbon material, and the peak positions are well matched with standard PDF cards (PDF # 41-1471).
Example 7
The cobalt disulfide/carbon composite electrode material prepared in example 1 was subjected to cyclic voltammetry testing and constant current charge and discharge testing in 6M KOH electrolyte.
Referring to fig. 7, in fig. 7, for cyclic voltammetry curves of the cobalt disulfide/carbon composite electrode material prepared in example 1 of the present invention measured at different sweep rates, significant redox peaks appear at positions around 0.45V and 0.35V, which shows significant pseudocapacitance characteristics. The shape of the curve remained essentially unchanged with increasing scan rate, and the redox peak of the cobalt disulfide/carbon composite electrode material of example 1 remained at a scan rate of 100mV/s, indicating that the cobalt disulfide/carbon composite electrode material had good stability and rate capability.
Referring to fig. 8, a constant current charging and discharging curve of the cobalt disulfide/carbon composite electrode material prepared in embodiment 1 of the present invention measured under different current densities is shown, and in fig. 8, a stable voltage platform appears at a position of 0.2 to 0.3V, which is a characteristic platform of the pseudocapacitance material. Under the current density of 1A/g, the specific capacity of the cobalt disulfide/carbon composite electrode material in the embodiment 1 reaches 595F/g. Under the current density of 10A/g, the specific capacity of the cobalt disulfide/carbon composite electrode material in the embodiment 1 reaches 536F/g. The capacity retention rate reaches 90%, which shows that the cobalt disulfide/carbon composite electrode material in the embodiment 1 has good stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The metal sulfide/carbon composite electrode material is characterized in that the metal sulfide/carbon composite electrode material is of a bowl-shaped structure;
the metal sulfide/carbon composite electrode material includes carbon and a metal sulfide doped in the carbon.
2. The sulfide/carbon composite electrode material according to claim 1, wherein the metal in the metal sulfide is a transition metal;
the transition metal is selected from one or more of cobalt, nickel, manganese, tin and molybdenum.
3. The sulfide/carbon composite electrode material according to claim 1, wherein the mass ratio of the metal sulfide to the carbon is 1: (4-10).
4. The sulfide/carbon composite electrode material according to claim 1, wherein the bowl-shaped structure has a bowl opening diameter of 170nm to 200 nm.
5. A preparation method of a metal sulfide/carbon composite electrode material is characterized by comprising the following steps:
a) adding microspheres, metal salt and organic resin into a solvent, and stirring and ultrasonically treating to obtain a first product;
b) drying the first product, and carbonizing in an inert atmosphere and/or a nitrogen atmosphere to obtain a second product;
c) etching the second product, and drying to obtain a third product;
d) and carrying out a vulcanization reaction on the third product and the sublimed sulfur in an inert atmosphere and/or a nitrogen atmosphere to obtain the bowl-shaped metal sulfide/carbon composite electrode material.
6. The method of claim 5, wherein the microspheres are SiO2Microspheres or polystyrene microspheres;
the metal salt is selected from one or more of cobalt salt, nickel salt, manganese salt, tin salt and molybdenum salt;
the organic resin is selected from one or more of PVDF, PAA and PVA.
7. The method of claim 6, wherein the microspheres are SiO2The metal salt is cobalt acetate, and the organic resin is PVDF;
the mass ratio of the microspheres to the metal salt to the organic resin is 1: (1-3): (1-3).
8. The preparation method according to claim 5, wherein the temperature rise rate of the carbonization in the step b) is 2 to 10 ℃/min;
the carbonization heat preservation temperature is 500-800 ℃;
the carbonization heat preservation time is 2-3 h.
9. The method according to claim 5, wherein the mass ratio of the third product of step d) to the sublimed sulfur is 1: (10-40);
the temperature rise rate of the vulcanization reaction is 2-5 ℃/min;
the heat preservation temperature of the vulcanization reaction is 300-500 ℃;
the heat preservation time of the vulcanization reaction is 3-6 h.
10. Use of the metal sulfide/carbon composite electrode material according to any one of claims 1 to 4 and/or the metal sulfide/carbon composite electrode material prepared by the preparation method according to any one of claims 5 to 9 in the field of energy storage.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563500A (en) * 2020-12-04 2021-03-26 广东工业大学 Preparation method of hollow bowl-shaped carbon-based metal/selenium/oxygen co-doped composite material and lithium ion battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098151A (en) * 2015-06-19 2015-11-25 上海交通大学 Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof
CN107369822A (en) * 2017-07-19 2017-11-21 广东工业大学 A kind of tin oxide/C nano hollow ball material as negative electrode of lithium ion battery and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098151A (en) * 2015-06-19 2015-11-25 上海交通大学 Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof
CN107369822A (en) * 2017-07-19 2017-11-21 广东工业大学 A kind of tin oxide/C nano hollow ball material as negative electrode of lithium ion battery and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUNHONG CHEN等: "Shape Engineering of Biomass-Derived Nanoparticles from Hollow Spheres to Bowls through Solvent-Induced Buckling", 《CHEMSUSCHEM》 *
SHENG CHEN等: "CoS nanosheets wrapping on bowl-like hollow carbon spheres with enhanced compact density for sodium-ion batteries", 《NANOTECHNOLOGY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563500A (en) * 2020-12-04 2021-03-26 广东工业大学 Preparation method of hollow bowl-shaped carbon-based metal/selenium/oxygen co-doped composite material and lithium ion battery

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