CN112054217A - CoSe2/C composite material and preparation method and application thereof - Google Patents
CoSe2/C composite material and preparation method and application thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
Abstract
The invention provides a CoSe2a/C composite material, a preparation method and application thereof. CoSe of the invention2The preparation method of the/C composite material comprises the steps of selecting a specific carbon material with a structure with a large specific surface area and a nano particle size as a carrier, anchoring cobalt ions on the surface of carbon particles under the action of a precipitator to form carbon-supported cobalt precursor nano particles, and converting the carbon-supported cobalt precursor nano particles into CoSe after high-temperature selenization reaction2The material does not have obvious agglomeration, has a 5-10 nm nanoparticle structure, has better conductivity and higher specific surface area, can expose more active sites, and improves CoSe2Oxygen reduction and oxygen evolution catalytic properties of/C composites for use as zinc-airThe battery material has good electrochemical performance; at the same time, the anchoring effect between the carbon and the cobalt selenide also enhances the cycling stability of the zinc-air battery.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to CoSe2a/C composite material, a preparation method and application thereof.
Background
With the continuous increase of the demand of people for high-quality and economical renewable energy, sustainable energy is provided, environmental pollution is reduced, and the development of energy conversion and storage systems with high cost performance and high efficiency is raised to the strategic level. New generation of energy storage devices, e.g. super capacitors, Li+/Na+/Zn2+Both plasma cells and metal-air cells have undergone blowout-type development. Among them, zinc-air batteries are drawing attention because of their advantages such as low manufacturing cost, high energy density, good environmental protection performance, safety and reliability. However, the slow rate of Oxygen Reduction Reaction (ORR) during discharge and Oxygen Evolution Reaction (OER) during charge of zinc-air batteries has hindered the large scale application of zinc-air batteries due to the lack of an efficient dual-function oxygen reduction-oxygen evolution electrocatalyst. In addition, the noble metal catalyst has problems of limited reserves, high price, poor durability, etc., which prevent its commercial application in the field of zinc-air batteries. At present, Pt-based and Ir/Ru-based noble metal catalyst materials are widely used as benchmark catalysts for ORR and OER, respectively, but neither of them can effectively drive the reverse reaction, which limits their application as dual-function catalysts for ORR and OER.
In recent years, CoSe2Because it is cheap and more efficient to catalyze the OER reaction, it is widely studied. Researchers have prepared CoSe of different sizes by different synthetic methods2And the chemical property of the catalyst in catalyzing ORR or OER reaction is explored. Zhang et al (Chenyun Z, Bingwei X, Shengfu D, et al. controllable 1D and 2D Cobalt Oxide and Cobalt Oxide nanostruct Nanostructures as high yield efficiency electrolytes for the Oxygen Evolution Reaction [ J]Chemistry-An Asian Journal,2018,13.) with Co (NO)3)21D nanowire-shaped CoSe with the average length of 90nm and the average width of 21nm is prepared by a hydrothermal synthesis method as a reactant2And an average area of 0.72 μm22D nanosheet CoSe2And measureThe OER electrocatalytic performance of the catalyst is tested; zhao et al (Zhao Yuan, Zhang Chuanxiang, Fan Rong, et al. selenium purified Reduced Graphene Oxide supplied Cose2 Nanoparticles as Efficient Electrochemical Catalyst for the Oxygen Reduction Reaction[J]ChemElectrochem,2018.) with Co (AC)2·4H2O is used as a reactant, and a hydrothermal synthesis method is adopted to prepare the selenium-doped graphene oxide loaded cobalt selenide particle composite material (CoSe)2Se-rGO), wherein the supported cobalt selenide particles had an average size of 81nm and were tested for ORR electrocatalytic performance; zhang et al (Zhang K, et al, Zinc Substistition-Induced Subtle laser diagnosis media the Active Center of Cobalt depletion electrodes for Enhanced Oxygen Evolution [ J]Small,2020,16(11): 1907001) cobalt selenide nanosheets 5 μm in length and 200nm in width were grown free-standing by hydrothermal method on foamed cobalt as substrate and tested for their OER performance. However, the prior art does not address the problem of dual-function ORR and OER catalysis.
Therefore, it is required to develop a bifunctional catalyst capable of catalyzing both the ORR reaction and the OER reaction, which has high catalytic activity during charging and discharging processes when applied to a zinc-air battery.
Disclosure of Invention
The invention aims to overcome the defect that CoSe exists in the existing zinc-air battery catalyst2As a catalyst, can only catalyze the defect of reaction activity of ORR or OER, provides a CoSe2A preparation method of the/C composite material. The invention selects the specific surface area of 800-1300 m2Per g, particle diameter of<Carbon material of 30nm as carrier can support CoSe2The particle size of the particles reaches 5-10 nm, the particles are uniformly loaded on the surface of the carbon material, more active sites are exposed, and CoSe is improved2Oxygen reduction and oxygen precipitation catalytic performance of/C composite material, and CoSe prepared by using the same2the/C composite material has higher catalytic activity in ORR and OER reactions, and has good electrical property when used as a zinc-air battery; at the same time, the anchoring effect between carbon and cobalt also improves the cycling stability of the zinc-air battery.
Hair brushAnother object of the invention is to provide CoSe prepared by the preparation method2a/C composite material. It is another object of the present invention to provide the CoSe2The application of the/C composite material in preparing a zinc-air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
CoSe2The preparation method of the/C composite material comprises the following steps:
s1, mixing a cobalt source, a carbon material and a precipitator in a solvent to perform a solvothermal reaction to obtain a carbon-supported cobalt precursor;
s2, calcining the carbon-supported cobalt precursor and the selenium source obtained in the step S1 under the inert gas condition to obtain the CoSe2a/C composite material;
the specific surface area of the carbon material is 300-1500 m2A particle diameter of the carbon material is<30nm。
CoSe of the invention2The preparation method of the/C composite material comprises the steps of selecting a specific carbon material with a structure with a large specific surface area and a nano particle size as a carrier, anchoring cobalt ions on the surface of carbon particles under the action of a precipitator to form carbon-supported cobalt precursor nano particles, and converting the carbon-supported cobalt precursor nano particles into CoSe after high-temperature selenization reaction2The material does not have obvious agglomeration, has a 5-10 nm nanoparticle structure, has better conductivity and higher specific surface area, can expose more active sites, and improves CoSe2The oxygen reduction and oxygen precipitation catalytic performance of the/C composite material has good electrochemical performance when being used as a zinc-air battery material; at the same time, the anchoring effect between the carbon and the cobalt selenide also enhances the cycling stability of the zinc-air battery.
Preferably, the cobalt source is one or a combination of several of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
Preferably, the precipitant is one or more of soluble carbonate, soluble bicarbonate, soluble hydroxide, urea, ammonia water or hexamethylenetetramine.
Preferably, the carbon material is one or a combination of several of ketjen black, CABOT 2000, superconducting carbon black or black Yu carbon black.
Preferably, the particle size of the carbon material is 10 to 20 nm.
Preferably, the solvent is one or a combination of several of deionized water, methanol, ethanol, isopropanol or n-butanol.
Preferably, the molar ratio of the cobalt source to the carbon material is 1: 50-300.
Preferably, the molar ratio of the cobalt source to the precipitant is 1: 10-100.
Preferably, the temperature of the solvothermal reaction is 100-180 ℃.
Preferably, the solvothermal reaction time is 6-24 h.
Preferably, the selenium source is one or a combination of several of selenium powder, selenite, selenium dioxide and selenosulfate.
Preferably, the mass ratio of the carbon-supported cobalt-based precursor to the selenium source is 1: 1-10.
Preferably, the calcining temperature is 350-450 ℃.
Preferably, the temperature rise rate of the calcination is 5-10 ℃/min.
Preferably, the calcining time is 2-12 h.
Preferably, the inert gas is N2And one or more of Ar or He.
Preferably, the flow rate of the inert gas is 25-300 mL/min.
CoSe2the/C composite material is prepared by the preparation method.
The CoSe2In the/C composite, CoSe2The particle size of the particles is 5-10 nm.
The CoSe2In the/C composite, CoSe2The loading amount of the catalyst is 10-30%.
The above CoSe2The use of the/C composite material for producing zinc-air batteries is also within the scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
hair brushBright CoSe2The preparation method of the/C composite material comprises the steps of selecting a specific carbon material with a structure with a large specific surface area and a nano particle size as a carrier, anchoring cobalt ions on the surface of carbon particles under the action of a precipitator to form carbon-supported cobalt precursor nano particles, and converting the carbon-supported cobalt precursor nano particles into CoSe after high-temperature selenization reaction2The material does not have obvious agglomeration, has a 5-10 nm nanoparticle structure, has better conductivity and higher specific surface area, can expose more active sites, and improves CoSe2The oxygen reduction and oxygen precipitation catalytic performance of the/C composite material has good electrochemical performance when being used as a zinc-air battery material; at the same time, the anchoring effect between the carbon and the cobalt selenide also enhances the cycling stability of the zinc-air battery. It is at 10mA/cm2The potential difference (Δ E) between the OER potential obtained at this point and the half-wave potential in the ORR is only 74 mV; meanwhile, after the zinc-air battery is prepared, the open-circuit potential is 1.518V, which is relatively close to the theoretical voltage of 1.65V, and the anchoring effect between carbon and cobalt also improves the cycling stability of the zinc-air battery, and the activity of the zinc-air battery can still reach more than 89% after 24h reaction. The preparation method of the invention also has the advantages of wide raw material source, low price, simple process, short experimental period and good repeatability.
Drawings
FIG. 1 depicts CoSe obtained in example 12XRD patterns of the/C composite and the substrate carbon;
FIG. 2 depicts CoSe obtained in example 12Transmission electron microscopy of the/C composite;
FIG. 3 depicts CoSe obtained in example 12A catalytic oxygen reduction performance diagram of the/C composite material;
FIG. 4 depicts CoSe obtained in example 12An oxygen reduction catalytic stability diagram for the/C composite;
FIG. 5 depicts CoSe obtained in example 12A performance diagram of the catalytic oxygen evolution of the/C composite;
FIG. 6 depicts CoSe obtained in example 12An oxygen evolution catalytic stability diagram of the/C composite;
FIG. 7 is CoSe obtained in comparative example 12Composite material/CTransmission electron microscopy images of (a).
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Table 1 shows specific surface areas and particle diameters of carbon materials used in examples of the present invention and comparative examples, which were obtained by actual tests.
TABLE 1 specific surface area and particle size of carbon materials for examples and comparative examples
Example 1
The present embodiment provides a CoSe2The electrical performance of the/C composite material and the zinc-air battery prepared from the same is tested.
S1, uniformly mixing 23.3mg of cobalt nitrate, 100mg of urea and 70mg of Ketjen black in 15mL of deionized water, stirring for 30min, transferring to a 25mL polytetrafluoroethylene reaction kettle, packaging with a stainless steel outer lining, and reacting in an oven at a constant temperature of 120 ℃ for 12 h. After the reaction is finished, cooling to room temperature, centrifuging and alternately washing for three times by using deionized water and ethanol, and then drying at 60 ℃ for 12h to obtain the carbon-supported cobalt-based precursor.
S2, weighing 0.1g of the carbon-supported cobalt-based precursor and 0.25g of selenium powder, placing the carbon-supported cobalt-based precursor and the selenium powder in a tubular furnace, continuously introducing air for 30min at an argon flow rate of 50mL/min to ensure that the inside of the tubular furnace is completely filled with nitrogen, then heating to 350 ℃ from room temperature at a heating rate of 2 ℃/min, maintaining the constant temperature for 4h, cooling to room temperature after calcination is finished, and obtaining 24.7% CoSe2a/C composite material.
Example 2
S1, uniformly mixing 15.2mg of cobalt chloride, 67mg of sodium bicarbonate and 48mg of CABOT 2000 in 15mL of ethanol, stirring for 30min, transferring to a 25mL polytetrafluoroethylene reaction kettle, packaging with a stainless steel outer lining, and reacting in an oven at a constant temperature of 100 ℃ for 24 h. After the reaction is finished, cooling to room temperature, centrifuging and alternately washing for three times by using deionized water and ethanol, and then drying at 60 ℃ for 12h to obtain the carbon-supported cobalt-based precursor.
S2, weighing 0.1g of the carbon-supported cobalt-based precursor and 1g of sodium selenite, placing the carbon-supported cobalt-based precursor and the sodium selenite in a tubular furnace, continuously ventilating for 30min at a nitrogen flow rate of 300mL/min to ensure that the interior of the tubular furnace is completely filled with nitrogen, then heating from room temperature to 450 ℃ at a heating rate of 5 ℃/min, maintaining the constant temperature for 6h, cooling to room temperature after calcination is finished, and obtaining CoSe with a load of 28.8%2a/C composite material.
Example 3
S1, uniformly mixing 17.7mg of cobalt acetate, 20mg of sodium hydroxide and 120mg of black Yu carbon black in 15mL of deionized water, stirring for 30min, transferring to a 25mL polytetrafluoroethylene reaction kettle, packaging by using a stainless steel outer liner, and reacting in an oven at a constant temperature of 180 ℃ for 6 h. After the reaction is finished, cooling to room temperature, centrifuging and alternately washing for three times by using deionized water and ethanol, and then drying at 60 ℃ for 12h to obtain the carbon-supported cobalt-based precursor.
S2, weighing 0.1g of the carbon-supported cobalt-based precursor and 0.5g of sodium selenosulfate, placing the carbon-supported cobalt-based precursor and the 0.5g of sodium selenosulfate into a tubular furnace, continuously ventilating for 30min at a nitrogen flow rate of 200mL/min to ensure that the inside of the tubular furnace is completely filled with nitrogen, then heating to 450 ℃ from room temperature at a heating rate of 10 ℃/min, maintaining the constant temperature for 6h, cooling to room temperature after calcination is finished, and obtaining CoSe with a loading capacity of 12.8%2a/C composite material.
Example 4
S1, uniformly mixing 16.9mg of cobalt sulfate, 84.1mg of hexamethylenetetramine and 100mg of superconducting carbon black in 15mL of methanol, stirring for 30min, transferring to a 25mL polytetrafluoroethylene reaction kettle, packaging by using a stainless steel outer lining, and reacting in an oven at a constant temperature of 160 ℃ for 12 h. After the reaction is finished, cooling to room temperature, centrifuging and alternately washing for three times by using deionized water and ethanol, and then drying at 60 ℃ for 12h to obtain the carbon-supported cobalt-based precursor.
S2, weighing 0.1g of the carbon-supported cobalt-based precursor and 0.75g of selenium powder, and placing the precursor and the selenium powder in a tubular furnaceContinuously introducing gas for 30min at the argon flow rate of 50mL/min to ensure that the interior of the tube furnace is completely filled with nitrogen, then raising the temperature from room temperature to 350 ℃ at the temperature raising rate of 2 ℃/min, maintaining the constant temperature for 6h, cooling to room temperature after calcination is finished, and obtaining CoSe with the loading of 13.0%2a/C composite material.
Comparative example 1
This comparative example was carried out in the same manner as in example 1 except that the carbon material in example 1 was replaced with Vulcan XC-72, and CoSe having a loading of 24.7% was produced2a/C composite material.
And (3) performance testing:
1. structural characterization:
1) the products obtained in each example and comparative example were subjected to X-ray diffraction characterization and the results are shown in table 2 and fig. 1.
2) The obtained product was analyzed by transmission electron microscopy, and the test results are shown in table 2 and fig. 2.
2. Preparing a zinc-air battery:
preparing a zinc-air battery: CoSe provided by each example and comparative example2The zinc-air battery is prepared by using the/C composite material as a catalyst, and the specific process is as follows: catalyst slurry (2.5mg catalyst dispersed in 475. mu.L mixture of ethanol and 25. mu.L 5 wt.% naphthol) was coated on a stainless steel mesh with an air diffusion layer as an air electrode, with the catalyst loading controlled at 1mg/cm2The commercial zinc sheet is used as an anode, 6M KOH +0.2M Zn (Ac)2As an electrolyte.
1) Oxygen reduction electrocatalytic properties: ORR test is carried out in 0.1M KOH alkaline electrolyte, and oxygen is firstly introduced into the electrolyte for 30min to ensure that the electrolyte is saturated with oxygen. The activated catalyst was first swept using cyclic voltammetry and then tested using linear sweep voltammetry, setting the rotating electrode speed at 1600 rpm. The test results are shown in table 2 and fig. 3.
2) Stability of oxygen reduction catalytic performance: ORR test is carried out in 0.1M KOH alkaline electrolyte, and oxygen is firstly introduced into the electrolyte for 30min to ensure that the electrolyte is saturated with oxygen. The ORR stability of the material was tested by chronoamperometry at a rotating electrode speed of 400rpm for a test time of 24 hours. The test results are shown in table 2 and fig. 4.
3) Oxygen evolution electrocatalytic properties: OER test is carried out in 1.0M KOH alkaline electrolyte, and oxygen is firstly introduced into the electrolyte for 30min to ensure that the electrolyte is saturated with oxygen. The activated catalyst was first swept using cyclic voltammetry and then tested using linear sweep voltammetry, setting the magnetic stirrer rotation speed at 400 rpm. The test results are shown in table 2 and fig. 5.
4) Stability of oxygen evolution catalytic performance: OER test is carried out in 1.0M KOH alkaline electrolyte, and oxygen is firstly introduced into the electrolyte for 30min to ensure that the electrolyte is saturated with oxygen. The OER stability of the material was tested using chronoamperometry with a magnetic stirrer speed of 400rpm for a test time of 24 h. The test results are shown in table 2 and fig. 6.
Table 2 results of performance test of each example and comparative example
As shown in table 2 and the X-ray diffraction results (fig. 1): as can be seen from fig. 1a, the substrate is a carbon material having a graphite structure; as can be seen from FIG. 1b, the diffraction peak corresponds to the orthorhombic CoSe system2JCPDS No.53-0449, FIG. 1b, CoSe prepared in example 12The XRD diffraction peak of the/C composite material consists of cobalt selenide and a substrate, and the cobalt selenide diffraction peak can be matched with a standard card thereof, so that the obtained product is CoSe2a/C composite material; the results of the other examples are similar to those of example 1.
As shown in table 2 and the transmission electron microscope analysis results (fig. 2): as can be seen from the figure, CoSe prepared in example 12The shape of the/C composite material is uniform nano particles, and the average size is 7 nm; as can be seen from Table 2, the CoSe prepared in examples 1-42The particle diameter of the/C composite material is below 10 nm.
From table 2 and fig. 3, it can be seen that: CoSe prepared in example 12The initial potential of the/C composite (curve 2) for catalytic oxygen reduction was 0.92V vs. RHE, half-wave potentialRHE at 0.84V vs. 5.8mA/cm2(ii) a After the cobalt selenide and the carbon material are physically mixed (curve 1), the initial potential for catalyzing oxygen reduction is 0.88V vs. RHE, the half-wave potential is 0.80V vs. RHE, and the limiting current density is 5.3mA/cm2Description of CoSe2Compared with a physical mixed catalyst of cobalt selenide and a carbon material, the performance of catalyzing oxygen reduction by the/C composite material is obviously improved. The results of the other examples are similar to those of example 1.
From table 2 and fig. 4, it can be seen that: CoSe prepared in example 12The activity of the/C composite material is still kept above 96% after 24 hours of reaction; while the activity decay of the physical hybrid catalyst (curve 2) was about 88%, the CoSe thus produced2the/C composite material (curve 1) has better catalytic stability for catalyzing oxygen reduction. The results of the other examples are similar to those of example 1.
From table 2 and fig. 5, it can be seen that: the initial potential for catalyzing oxygen evolution after cobalt selenide and carbon material were physically mixed (curve 2) was 1.58V vs. rhe, 10mA/cm2The overpotential of (A) is 1.67V vs. RHE; and CoSe prepared in example 12The initial potential of the/C composite (curve 1) for catalysing oxygen evolution was 1.45Vvs. RHE, 10mA/cm2The overpotential of the catalyst is 1.58V vs. RHE, and the performance indexes are all superior to those of a physical mixed catalyst, which shows that CoSe is2Compared with a physical mixed catalyst of cobalt selenide and a carbon material, the performance of catalyzing oxygen precipitation of the/C composite material is obviously improved. The results of the other examples are similar to those of example 1.
From table 2 and fig. 6, it can be seen that: CoSe prepared in example 12the/C composite (curve 1) still maintained more than 92% of activity after 24h reaction, while the activity of the physical hybrid catalyst (curve 2) decayed to about 84%, so that the CoSe prepared in example 12the/C composite material has excellent catalytic stability for catalyzing oxygen precipitation. The results of the other examples are similar to those of example 1.
As can be seen from the results in Table 2, CoSe prepared by the present invention2The oxygen precipitation catalytic activity of the/C composite material is at least improved by 8.5 percent compared with that of a comparative example; the catalytic activity of oxygen reduction is at least improved by 9.5 percent compared with that of the comparative example. Comparative example 1 selectionCarbon material Vulcan XC-72 with larger particle size (40-70 nm) is prepared to obtain CoSe2In the/C composite, CoSe2Connected into a rod-like structure due to the fact that the particle size of Vulcan XC-72 is larger than the particle size of the carbon material selected by the application (C<30nm), the anchoring effect of the loaded particles on the surface of the carbon material is weak, so that CoSe is subjected to high-temperature selenization reaction under the same addition amount2Agglomeration is formed on the surface of the carbon material (as shown in fig. 7), and exposed active sites are reduced, thereby further reducing the catalytic performance and stability of the carbon material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. CoSe2The preparation method of the/C composite material is characterized by comprising the following steps:
s1, mixing a cobalt source, a carbon material and a precipitator in a solvent to perform a solvothermal reaction to obtain a carbon-supported cobalt precursor;
s2, calcining the carbon-supported cobalt precursor and the selenium source obtained in the step S1 under the inert gas condition to obtain the CoSe2a/C composite material;
the specific surface area of the carbon material is 300-1500 m2A particle diameter of the carbon material is<30nm。
2. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the particle size of the carbon material is 10-20 nm.
3. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the cobalt source is one or a combination of more of cobalt acetate, cobalt nitrate, cobalt sulfate or cobalt chloride; the carbon materialIs one or the combination of more of Ketjen black, CABOT 2000, superconducting carbon black or black Yu carbon black; the precipitant is one or more of soluble carbonate, soluble bicarbonate, soluble hydroxide, urea, ammonia water or hexamethylenetetramine; the selenium source is one or more of selenium powder, selenite, selenium dioxide or selenosulfate.
4. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the molar ratio of the cobalt source to the carbon material is 1: 50-300; the molar ratio of the cobalt source to the precipitant is 1: 10-100.
5. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the temperature of the solvothermal reaction is 100-180 ℃; the solvothermal reaction time is 6-24 h.
6. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the mass ratio of the carbon-supported cobalt-based precursor to the selenium source is 1: 1-10.
7. The CoSe of claim 12The preparation method of the/C composite material is characterized in that the calcining temperature is 350-450 ℃; the calcining time is 2-12 h.
8. CoSe2the/C composite material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The CoSe of claim 82a/C composite, characterized in that the CoSe is2CoSe in/C composite material2The particle size of the particles is 5-10 nm; the CoSe2CoSe in/C composite material2The loading amount of the catalyst is 10-30%.
10. Any of claims 8 to 9The CoSe2The application of the/C composite material in preparing a zinc-air battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113611861A (en) * | 2021-07-26 | 2021-11-05 | 江苏智泰新能源科技有限公司 | Nitrogen-doped CoSe2Preparation method and application of |
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