CN118099348A - Nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, and preparation method and application thereof - Google Patents
Nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, and preparation method and application thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 145
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 dimethyl imidazole cobalt Chemical compound 0.000 claims abstract description 45
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- 238000003756 stirring Methods 0.000 claims description 22
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- 238000002156 mixing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
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- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 34
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- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
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- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 30
- 239000011261 inert gas Substances 0.000 description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 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 14
- 239000011812 mixed powder Substances 0.000 description 14
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 13
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- 238000001228 spectrum Methods 0.000 description 11
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present disclosure relates to a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material, a preparation method and an application thereof, wherein the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material is formed by doping tricobalt tetraselenide nanoparticles on a nitrogen-doped carbon polyhedron and interconnecting the nitrogen-doped carbon polyhedron with a carbon nanotube as an electrode composite material to improve charge and discharge cycle capability, and the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material provides an electron transport channel with the carbon nanotube; the nitrogen doped carbon derived from the dimethyl imidazole cobalt is used as a carbon bracket, so that a stable polyhedral structure is provided and the conductivity is enhanced; the cobaltosic selenide is used as the transition metal selenide, so that the catalytic and adsorption capacities of the composite material are enhanced, and the cycle stability and the service life of the battery are improved. Meanwhile, the invention also provides a preparation method of the nitrogen-doped carbon/cobaltosic selenide/carbon nano tube, which has the advantages of simple production process and low cost, and the prepared nitrogen-doped carbon/cobaltosic selenide/carbon nano tube has excellent electrochemical performance.
Description
Technical Field
The disclosure relates to the technical field of advanced nanocomposite preparation, in particular to a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite, and a preparation method and application thereof.
Background
In recent years, lithium sulfur batteries have become a long-term research hot spot in the field of new energy storage/conversion by virtue of the advantages of ultrahigh specific capacity (1675 milliampere per gram), high theoretical energy density (2600 watt per kilogram), abundant sulfur storage, environmental protection, low price and the like, and are pointed out the direction for the development of the next-generation energy system, particularly the field of electric automobiles. The lithium-sulfur battery is a secondary battery which uses lithium as an anode and sulfur as a cathode to convert chemical energy provided by sulfur-sulfur bond cleavage into electric energy. Therefore, designing a sulfur host with high conductivity is an effective strategy to improve the cycling performance of lithium sulfur batteries.
Currently, extensive research is being conducted on various nanostructured carbonaceous materials. However, most carbon-based materials contain only a few polar sites, which results in fewer sites for binding to lithium polysulfide. Therefore, the conductivity, surface polarity and adsorption capacity of lithium polysulfide in carbon-based materials can be significantly improved by doping with heteroatoms, such as nitrogen, phosphorus and oxygen atoms. In recent years, porous carbon materials synthesized by carbonizing metal-organic framework materials have been attracting attention due to their high porosity and high specific surface area. The abundant organic ligands provide a rich carbon source, and the formed porous carbon is favorable for the adsorption of lithium polysulfide due to the unique morphology and layered porous structure of the porous carbon. Dimethyl imidazole cobalt is a porous zeolite-like metal organic framework material composed of cobalt ion centers and dimethyl imidazole ligands. The cobalt-based electrocatalyst has better activity and chemical stability. In addition, cobalt particles on carbon-based materials significantly enhance electrocatalytic activity by increasing electron conductivity and providing more active sites. In addition to the direct formation of cobalt carbon bonds, there is also a strong synergy between cobalt and carbon, which can further enhance catalytic activity. In addition, carbon nanotubes are considered to be a promising catalyst due to their simple preparation, good electrical conductivity, and excellent electrochemical activity. Through previous research work, it was found that metal organic framework materials are capable of obtaining carbon-based materials of large surface area and generating sufficient metal active sites for electrocatalysis. In addition, in metal-carbon composites derived from metal-organic frameworks, stronger coordination between the metal and carbon atoms can result in a strong framework. By sintering and migrating the in-situ formed metal nanoparticles, uniform distribution of heteroatoms and metal species in the framework is achieved. Cobalt-based compounds have received extensive attention in the past because of their high chemical stability and excellent electrical conductivity.
Cobalt-based chalcogenides exhibit excellent cycling performance in lithium sulfur battery systems due to their good catalytic action. Generally, transition metal selenides have higher electrical conductivity than their sulfides and show greater potential for use as catalysts in lithium sulfur batteries. As mentioned in prior art "'Ultrafine Co3Se4Nanoparticles in Nitrogen-Doped 3D Carbon Matrix for High-Stable and Long-Cycle-Life Lithium Sulfur Batteries',Cai D,Liu B K,Zhu D H,et al.Advanced Energy Materials,2020,10(19):1904273", by doping highly conductive and catalytic tricobalt tetraselenide nanoparticles in a nitrogen-doped three-dimensional interconnected carbon matrix, the dissolved lithium polysulfide diffuses and migrates to the lithium anode under competition of concentration gradient and electric field forces, being trapped by active n-doped sites and Co 3Se4 centers. The adsorbed lithium polysulfide can accept and release electrons at these polar sites through the adjacent conductive carbon, and the exposed carbon/Co 3Se4/electrolyte interface can accelerate the conversion reaction of these sulfur species, giving it good electrochemical properties. However, the restraint and catalysis of lithium polysulfide by transition metal selenide as an electrocatalyst is still in an early stage.
Disclosure of Invention
In order to overcome the defects in the prior art, the present disclosure provides a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material, and a preparation method and application thereof.
According to a first aspect of the present disclosure, there is provided a method for preparing a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite, characterized by comprising the steps of:
firstly, preparing dimethyl imidazole cobalt, respectively dissolving a cobalt source and dimethyl imidazole in a methanol solution according to a certain proportion, and fully stirring and mixing to obtain a mixed solution; placing the mixed solution in a beaker and aging the mixed solution in a normal temperature environment; washing, filtering and drying after the aging is finished to obtain purple powder, namely dimethyl imidazole cobalt powder;
preparing a nitrogen-doped carbon/cobalt/carbon nanotube, placing the dimethyl imidazole cobalt obtained in the first step into a beaker, adding a carbon source into an ethanol solution, fully stirring, and drying after stirring is completed; carbonizing the dried powder in a tube furnace under inert atmosphere to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
And thirdly, preparing the nitrogen-doped carbon/cobaltosic selenide/carbon nano tube, fully grinding and mixing the nitrogen-doped carbon/cobalt/carbon nano tube obtained in the second step with a selenium source according to a proportion, and then placing the mixture into a tube furnace for heat treatment under an inert atmosphere to obtain the nitrogen-doped carbon/cobaltosic selenide/carbon nano tube powder.
Preferably, the cobalt dimethylimidazole in the first step is one of metal organic structural materials, the cobalt source adopts cobalt nitrate, and the molar ratio of the cobalt source to the dimethylimidazole is 1:3-1:7.
Preferably, the aging temperature in the first step is 25 ℃ at normal temperature, and the aging time is 24 hours.
Preferably, the carbon nanotubes in the second step are derived from melamine, and the mass ratio of the dimethylcobalt imidazole to the melamine is 1:1-1:2.
Preferably, the carbonization in the second step is performed under the condition that the carbonization is performed for 2 hours at 500-570 ℃ and then performed for 2 hours at 700-810 ℃.
Preferably, in the third step, the selenium source is elemental selenium powder, and the mass ratio of the nitrogen-doped carbon/cobalt/carbon nanotube material to the selenium powder is 1:1-1:2.
Preferably, the heat treatment temperature in the third step is 600-680 ℃ and the heat treatment time is 5 hours.
According to a second aspect of the present disclosure, there is provided a nitrogen doped carbon/tricobalt tetraselenide/carbon nanotube composite.
According to a third aspect of the present disclosure there is provided the use of a nitrogen doped carbon/tricobalt tetraselenide/carbon nanocomposite.
The principle of the technical scheme of the disclosure is as follows:
The present disclosure provides a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material, a preparation method and application thereof, wherein a carbon nanotube is used for communicating with a nitrogen-doped carbon skeleton, so as to improve charge-discharge cycle capability of tricobalt tetraselenide, the carbon nanotube is used for providing an electron transport channel, nitrogen-doped carbon is used as a carbon support and providing nitrogen-doped sites, tricobalt tetraselenide is used as a catalytic and adsorption material, so as to enhance charge-discharge cycle performance of the composite material, and the charge-discharge cycle performance is one of batteries with lithium, sodium or potassium as an anode. Specifically, the dimethyl imidazole cobalt is carbonized to obtain a nitrogen-doped carbon skeleton, the porous carbon skeleton has high porosity and high specific surface area, and the nitrogen element doping improves the polarity and the sulfur affinity of the carbon skeleton; carbonizing melamine coated on dimethyl imidazole cobalt to obtain carbon nanotubes, wherein a large number of carbon nanotubes provide a transmission channel for electrons; the cobalt monose on the carbonized surface is selenized to obtain the tricobalt tetraselenide serving as a cobalt-based chalcogenide catalyst, so that the catalysis and adsorption capacities of the composite material are enhanced, and the cycle stability and the service life of the battery are improved.
The beneficial effects of the technical scheme of the disclosure are that:
1. The method for improving the charge-discharge circulation capacity of the tricobalt tetraselenide by utilizing the carbon nano tube to communicate with the nitrogen-doped carbon skeleton has the advantages of low cost, simple process and excellent electrochemical performance of the prepared nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, and the composite material provides an electron transmission channel by using the carbon nano tube; the nitrogen-doped carbon serves as a carbon support to provide a stable polyhedral structure and enhance conductivity; tricobalt tetraselenide as a transition metal selenide enhances catalytic and adsorptive capacity. The initial discharge capacity of the lithium-sulfur battery can reach 1413 milliampere hours per gram, 1039 milliampere hours per gram after 100 times of circulation, 1000 times of circulation can be continued under the current density of 1C, and the capacity attenuation rate of each circulation is 0.034%. Meanwhile, the rate performance is good under different current densities.
2. According to the nitrogen-doped carbon/cobaltosic selenide/carbon nanotube composite material, the dimethylimidazole cobalt is carbonized to obtain the nitrogen-doped carbon skeleton serving as a three-dimensional matrix material, the formed porous carbon skeleton has the characteristics of high porosity and high specific surface area, and the polarity and the sulfur affinity of the carbon skeleton are improved through nitrogen element doping, so that a guarantee is provided for the excellent electrochemical performance of the composite material; the melamine coated on the dimethyl imidazole cobalt is carbonized to obtain carbon nanotubes, and a large number of carbon nanotubes provide transmission channels for electrons, so that the electrochemical performance of the battery is improved; the cobalt tetra-selenide obtained by selenizing the cobalt simple substance on the carbonized surface is used as a cobalt-based chalcogenide catalyst, so that the catalysis and adsorption capacities of the composite material are enhanced, and the catalyst plays a key role in the aspects of the cycling stability, the service life and the like of the battery.
3. The present disclosure provides a method for preparing a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material, which is prepared by a precipitation method, a high-temperature carbonization method and a high-temperature melting method; specifically, dimethyl imidazole cobalt is synthesized through an aging reaction, then mixed with melamine, carbonized at a high temperature, and finally melted with selenium powder at a high temperature to obtain the composite material. The whole preparation method has simple process and low cost, and effectively reduces the experiment difficulty.
Drawings
The above and other features, advantages and aspects of embodiments of the present disclosure will become more apparent by reference to the following detailed description when taken in conjunction with the accompanying drawings. For a better understanding of the present disclosure, and without limiting the disclosure thereto, the same or similar reference numerals denote the same or similar elements, wherein: FIG. 1 is a schematic diagram of the synthesis of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite prepared according to an embodiment of the disclosure;
FIG. 2 is a scanning electron microscope of (a) dimethylimidazole cobalt, (b) nitrogen doped carbon/cobalt/carbon nanotube composite, (c) nitrogen doped carbon/tricobalt tetraselenide/carbon nanotube composite, and (d) nitrogen doped carbon/tricobalt tetraselenide/carbon nanotube composite;
FIG. 3 is a Raman spectrum of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube, nitrogen-doped carbon/tricobalt tetraselenide, and nitrogen-doped carbon/cobalt/carbon nanotube composite material prepared in an embodiment of the disclosure;
FIG. 4 is an X-ray diffraction pattern of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube, nitrogen-doped carbon/tricobalt tetraselenide, and nitrogen-doped carbon/cobalt/carbon nanotube composite material prepared in accordance with an embodiment of the present disclosure;
FIG. 5 is a full spectrum of an X-ray photoelectron spectrum (a) of a nitrogen doped carbon/tricobalt tetraselenide/carbon nanotube composite material prepared in an embodiment of the disclosure; (b) is a high resolution spectrum of carbon; (c) is a high resolution spectrum of nitrogen; (d) is a high resolution spectrum of cobalt; (e) is a high resolution spectrum of selenium;
FIG. 6 is a cycle chart of a lithium sulfur battery with a lithium electrode and a prepared nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube doped sulfur electrode according to an embodiment of the present disclosure;
FIG. 7 is a graph showing the rate performance of a lithium-sulfur battery with a prepared nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube-doped sulfur electrode according to an embodiment of the present disclosure at different current densities;
Fig. 8 is a long cycle graph of a lithium sulfur battery with a prepared nitrogen doped carbon/tricobalt tetraselenide/carbon nanotube doped sulfur electrode according to an embodiment of the disclosure.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present disclosure, and it is apparent that the described embodiments are only some embodiments of the present disclosure, not all embodiments. Based on the embodiments in this disclosure, all other embodiments that a person of ordinary skill in the art would obtain without making any inventive effort are within the scope of protection of this disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items. It is to be understood that the various materials in this disclosure are commercially available unless otherwise indicated.
Example 1
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Firstly, preparing dimethyl imidazole cobalt, putting 3.4933 g of cobalt nitrate hexahydrate into a beaker, adding 100 ml of methanol, and magnetically stirring for half an hour; 3.947 g of dimethyl imidazole are placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; pouring the dimethyl imidazole solution into the cobalt nitrate hexahydrate solution, mixing and stirring for 10 minutes, and then carrying out aging reaction for 24 hours at normal temperature; centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
Step two, preparing nitrogen doped carbon/cobalt/carbon nano tubes, putting 200 mg of dimethyl imidazole cobalt powder obtained in the step one and 200 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring is completed until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 550 ℃ for 2 hours, and then heating at 700 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:2 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 650 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Fig. 1 is a schematic diagram of the synthesis of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite prepared in an embodiment of the disclosure.
Fig. 2 is a scanning electron microscope image of (a) dimethylimidazole cobalt, (b) nitrogen-doped carbon/cobalt/carbon nanotube composite, (c) nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite, and (d) nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite. As can be seen from the scanning characterization, the dimethyl imidazole cobalt has a dodecahedron structure. The graph (b) is a nitrogen-doped carbon/cobalt/carbon nanotube composite material obtained by carbonization after melamine coating, has a polyhedral structure similar to a precursor, has a shrinkage phenomenon on the surface, and is formed by carbon nanotubes. The graph (c) is a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material obtained through selenization, and has a polyhedral structure, and a plurality of mutually connected tiny tubular structures and tiny nano particles appear on the surface. And the graph (d) is a transmission electron microscope graph of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, and a large number of carbon nano tubes and fine nano particles covered on the surface of the polyhedron can be seen.
FIG. 3 is a Raman spectrum of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube, nitrogen-doped carbon/tricobalt tetraselenide, and nitrogen-doped carbon/cobalt/carbon nanotube composite material prepared in an embodiment of the disclosure; the graph shows that the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material has obvious graphite peak and amorphous carbon peak, and the I D/IG ratio is the largest, so that compared with the other two materials, the composite material has the largest defects.
FIG. 4 is an X-ray diffraction pattern of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube, nitrogen-doped carbon/tricobalt tetraselenide, and nitrogen-doped carbon/cobalt/carbon nanotube composite material prepared in accordance with an embodiment of the present disclosure; it can be seen from the graph that all peaks of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes and the nitrogen-doped carbon/tricobalt tetraselenide correspond well to characteristic peaks of tricobalt tetraselenide, while characteristic peaks of the nitrogen-doped carbon/cobalt/carbon nanotubes correspond well to elemental cobalt. Meanwhile, it was observed that the nitrogen-doped carbon/cobalt/carbon nanotubes showed (111), (200) and (220) crystal planes, and the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes showed (111), (311) and (31-3) crystal planes. For these three samples, no significant carbon peaks were seen due to the low carbon content and in the amorphous state.
FIG. 5 (a) is a full spectrum of the X-ray photoelectron spectrum of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material prepared in this example; as can be seen from the figure, the material contains carbon element, nitrogen element, oxygen element, cobalt element and selenium element. 5 (b) to (e) are respectively the high-resolution spectrum of carbon, the high-resolution spectrum of nitrogen, the high-resolution spectrum of cobalt and the high-resolution spectrum of selenium of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite material. From 5 (b) it can be seen that carbon is present in the form of C-C/c=c (284.6 eV), C-N/C-Se (285.4 eV) and C-O (286.6 eV). Nitrogen is present in the form of pyridine nitrogen (398.1 eV), pyrrolidine nitrogen (400.1 eV), graphite nitrogen (400.8 eV) and nitrogen oxide (403.9 eV). According to the high resolution spectrum of cobalt, the binding energies of the divalent and trivalent states of cobalt are located at positions 781.6 and 778.7eV, respectively. In the high resolution selenium photoelectron spectrum, the fitted peaks at binding energies of 56.1 and 55.3eV are assigned to the 3d 3/2 and 3d 5/2 orbitals of selenium, respectively.
FIG. 6 is a cycle chart of a lithium-sulfur battery with a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube doped sulfur as the electrode prepared in example one; the charge-discharge cycle was performed at a current density of 0.12C, and the initial discharge capacity was 1413 milliamp hours per gram, and after 100 cycles, the discharge capacity was 1039 milliamp hours per gram. And has good circulation stability, capacity retention rate is 74% after 100 times of circulation, and coulombic efficiency is as high as 99.4% after circulation.
FIG. 7 is a graph showing the rate performance of a lithium-sulfur battery with a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube doped sulfur as an electrode and prepared in accordance with the first embodiment at different current densities; at current densities of 0.1, 0.3, 0.5, 1, and 2C, the initial discharge capacities were 1414, 1150, 1052, 966, and 758 milliamp hours per gram, respectively. When the current density was reduced from 2C to 0.1C, the reversible discharge capacity returned to 1202 milliamperes per gram, indicating good rate performance.
FIG. 8 is a graph showing the long-cycle of a lithium-sulfur battery with a nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube doped sulfur electrode prepared in accordance with the first embodiment; 1000 charge and discharge cycles were performed at a current density of 1C. The initial discharge capacity is 1095 milliampere hours per gram, and the discharge capacity is still kept at 629 milliampere hours per gram after 1000 cycles, and the capacity attenuation rate of each cycle is 0.034%.
Example 2
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Step one, preparing dimethyl imidazole cobalt: 3.516 g of cobalt nitrate hexahydrate is placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; 5.978 g of dimethylimidazole were placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
Step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; 148 mg of the dimethylimidazole cobalt powder obtained in the first step and 152 mg of melamine are placed in a beaker, 50 ml of ethanol is added, stirring is carried out for 12 hours in an environment of 25 ℃, and the mixture is dried in an oven of 60 ℃ after the stirring is finished until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 500 ℃ for 2 hours, and then heating at 700 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:2 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 650 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Example 3
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Step one, preparing dimethyl imidazole cobalt: 1.749 g of cobalt nitrate hexahydrate is placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; 1.876 g of dimethylimidazole were placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
Step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; putting 124 mg of the dimethylimidazole cobalt powder obtained in the first step and 250 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 520 ℃ for 2 hours, and then heating at 750 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:2 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 600 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Example 4
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Step one, preparing dimethyl imidazole cobalt: 3.478 g of cobalt nitrate hexahydrate is placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; 3.876 g of dimethylimidazole were placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; putting 136 mg of the dimethylimidazole cobalt powder obtained in the first step and 278 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 530 ℃ for 2 hours, and then heating at 800 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:2 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 630 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Example 5
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Step one, preparing dimethyl imidazole cobalt: 1.728 g of cobalt nitrate hexahydrate was placed in a beaker, 100 ml of methanol was added, and the mixture was magnetically stirred for half an hour; 2.987 g of dimethylimidazole were placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
Step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; putting 217 mg of the dimethylimidazole cobalt powder obtained in the first step and 226 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 515 ℃ for 2 hours, and then heating at 740 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:1 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 610 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Example 6
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
step one, preparing dimethyl imidazole cobalt: 3.684 g of cobalt nitrate hexahydrate is placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; 6.103 g of dimethylimidazole were placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; putting 167 mg of the dimethylimidazole cobalt powder obtained in the first step and 341 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 560 ℃ for 2 hours, and then heating at 780 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:2 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 670 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
Example 7
The embodiment of the disclosure provides a preparation method of a nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material, which comprises the following steps:
Step one, preparing dimethyl imidazole cobalt: 1.776 g of cobalt nitrate hexahydrate is placed in a beaker, 100 ml of methanol is added, and the mixture is magnetically stirred for half an hour; 2.135 g of dimethylimidazole was placed in a beaker, 100 ml of methanol was added and magnetically stirred for half an hour. The dimethyl imidazole solution is poured into the cobalt nitrate hexahydrate solution, mixed and stirred for 10 minutes, and then the aging reaction is carried out for 24 hours under the normal temperature condition. Centrifuging and collecting the aged solution in ethanol solution for 3 times to obtain a precipitate, and drying the precipitate in an oven at 60 ℃ for 12 hours to remove water to obtain dried purple dimethyl imidazole cobalt powder;
Step two, preparing a nitrogen-doped carbon/cobalt/carbon nano tube; putting 237 mg of the dimethylimidazole cobalt powder obtained in the first step and 483 mg of melamine into a beaker, adding 50 ml of ethanol, stirring for 12 hours in an environment of 25 ℃, and drying in an oven of 60 ℃ after stirring until the moisture is completely evaporated; placing the dried solid powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, adjusting inert gas for protection, heating at 570 ℃ for 2 hours, and then heating at 810 ℃ for 2 hours for thermal reaction to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
Step three, preparing a nitrogen-doped carbon/cobaltosic selenide/carbon nano tube; mixing the nitrogen-doped carbon/cobalt/carbon nanotube powder obtained in the second step with selenium powder according to the mass ratio of 1:1 are put into a mortar and ground for 20 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 680 ℃, heating the porcelain boat for 5 hours, and performing thermal reaction to obtain the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube powder.
In some embodiments, sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotubes are prepared; mixing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder obtained in the step three with sublimed sulfur according to the mass ratio of 1:3, putting the mixture into a mortar, and grinding the mixture for 30 minutes to uniformly mix the two powders. And (3) placing the mixed powder into a porcelain boat, placing the porcelain boat into a tube furnace, setting a temperature program, protecting the porcelain boat by inert gas at 155 ℃, heating the porcelain boat for 12 hours, and performing thermal reaction to obtain the sulfur-doped nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube powder.
While the fundamental principles and main features of the present disclosure and advantages thereof have been shown and described, it will be apparent to those skilled in the art that the present disclosure is not limited to the details of the above-described exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential features thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the disclosure being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. The preparation method of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material is characterized by comprising the following steps of:
firstly, preparing dimethyl imidazole cobalt, respectively dissolving a cobalt source and dimethyl imidazole in a methanol solution according to a certain proportion, and fully stirring and mixing to obtain a mixed solution; placing the mixed solution in a beaker and aging the mixed solution in a normal temperature environment; washing, filtering and drying after the aging is finished to obtain purple powder, namely dimethyl imidazole cobalt powder;
preparing a nitrogen-doped carbon/cobalt/carbon nanotube, placing the dimethyl imidazole cobalt obtained in the first step into a beaker, adding a carbon source into an ethanol solution, fully stirring, and drying after stirring is completed; carbonizing the dried powder in a tube furnace under inert atmosphere to obtain black nitrogen-doped carbon/cobalt/carbon nanotube powder;
And thirdly, preparing the nitrogen-doped carbon/cobaltosic selenide/carbon nano tube, fully grinding and mixing the nitrogen-doped carbon/cobalt/carbon nano tube obtained in the second step with a selenium source according to a proportion, and then placing the mixture into a tube furnace for heat treatment under an inert atmosphere to obtain the nitrogen-doped carbon/cobaltosic selenide/carbon nano tube powder.
2. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
The cobalt dimethylimidazole in the first step is one of metal organic structural materials, the cobalt source is cobalt nitrate, and the molar ratio of the cobalt source to the dimethylimidazole is 1:3-1:7.
3. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
The ageing temperature in the first step is 25 ℃ at normal temperature, and the ageing time is 24 hours.
4. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
The carbon nano tube in the second step is derived from melamine, and the mass ratio of the dimethyl imidazole cobalt to the melamine is 1:1-1:2.
5. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
The carbonization condition in the second step is that the carbonization is firstly carried out for 2 hours at 500-570 ℃ and then carried out for 2 hours at 700-810 ℃.
6. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
In the third step, the selenium source adopts elemental selenium powder, and the mass ratio of the nitrogen-doped carbon/cobalt/carbon nanotube material to the selenium powder is 1:1-1:2.
7. The method for preparing the nitrogen-doped carbon/tricobalt tetraselenide/carbon nano tube composite material according to claim 1, wherein,
And in the third step, the heat treatment temperature is 600-680 ℃ and the heat treatment time is 5 hours.
8. A nitrogen-doped carbon/tricobalt tetraselenide/carbon nanotube composite obtainable by the process according to any one of claims 1 to 7.
9. Use of the nitrogen-doped carbon/tricobalt tetraselenide/carbon nanocomposite according to claim 8.
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