CN114229805A - Preparation method and application of nitrogen-doped porous carbon-coated cobalt diselenide composite material - Google Patents
Preparation method and application of nitrogen-doped porous carbon-coated cobalt diselenide composite material Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a nitrogen-doped porous carbon-coated cobalt diselenide composite material, wherein the preparation method comprises the following steps: respectively dissolving cobalt salt and selenium powder in a solvent, and stirring for the first time to respectively obtain a cobalt salt solution and a selenium powder solution; pouring the selenium powder solution into the cobalt salt solution, adding the liquid acrylonitrile oligomer, stirring for the second time, and adding the hydrazine hydrate solution after stirring to obtain a mixed solution; transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction, and then cooling, centrifuging and drying to obtain a precipitate; and calcining the precipitate, cooling, grinding and sieving to obtain the nitrogen-doped porous carbon-coated cobalt diselenide composite material. The prepared nitrogen-doped porous carbon-coated cobalt diselenide composite material is prepared into a lithium ion battery cathode, and the discharge specific capacity of 644mAh/g is still obtained after 300 charge-discharge cycles under the current density of 0.2A/g.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method and application of a nitrogen-doped porous carbon-coated cobalt diselenide composite material.
Background
Lithium ion batteries have attracted much attention due to their excellent characteristics of high operating voltage, high energy efficiency, long cycle life, and cleanliness and environmental protection, and are the most widely used type of energy storage devices in the market today. The Transition Metal Chalcogenide (TMCs) has good lithium storage performance and high safety performance. Can be used as the cathode material of the lithium ion battery. Such as cobalt selenide and compounds thereof, exhibit excellent performance in energy storage devices such as hybrid vehicles, portable electronic devices, and the like. The transition metal chalcogenide is used as a novel lithium ion battery cathode material and has the advantages of high theoretical capacity, low potential platform, relatively high electrochemical activity and the like. And according to different preparation methods and synthesis conditions, the transition metal chalcogenide can show different morphologies, the particle size and specific surface of the material can be regulated and controlled in a large range, and the electrochemical performance of the material can be correspondingly improved by improving the structural stability of the material. In addition, metal selenides have relatively high electron conductivity and low energy conversion reactions compared to metal sulfides, and thus exhibit longer cycle life. The selenium (Se) element has higher volume energy density, so that the metal selenide has more excellent electrochemical performance.
Coating by a carbon layer is a common method for improving electrochemical properties of selenides, but there are also problems of incomplete coating, insufficient volume expansion limitation, particle pulverization, and the like. Accordingly, the prior art remains to be improved and developed.
Disclosure of Invention
The invention provides a preparation method and application of a nitrogen-doped porous carbon-coated cobalt diselenide composite material, and aims to relieve volume expansion of a cobalt diselenide material and improve the conductivity of the material and the diffusion coefficient of lithium ions, so that the rate capability and the charge-discharge cycle performance of the material are improved, and technical support is provided for application of a novel negative electrode material of a lithium ion battery with high power density and high energy density.
The technical scheme for solving the technical problems is as follows:
the invention provides a preparation method of a nitrogen-doped porous carbon-coated cobalt diselenide composite material, which comprises the following steps:
s1, respectively dissolving cobalt salt and selenium powder in a solvent, and stirring for the first time to respectively obtain a cobalt salt solution and a selenium powder solution;
s2, pouring the selenium powder solution into the cobalt salt solution, adding liquid acrylonitrile oligomer (serving as a carbon source and a nitrogen source), stirring for the second time, and adding a hydrazine hydrate solution (serving as a nitrogen source) after stirring to obtain a mixed solution;
s3, transferring the mixed solution to a hydrothermal reaction kettle for hydrothermal reaction, and then cooling, centrifuging and drying to obtain a precipitate;
and S4, calcining the precipitate, cooling, grinding and sieving to obtain the nitrogen-doped porous carbon-coated cobalt diselenide composite material.
The invention adopts selenium powder and cobalt salt to react to generate cobalt diselenide, and utilizes liquid acrylonitrile oligomer in-situ polymerization to coat the generated cobalt diselenide particles to prepare the nitrogen-doped porous carbon-coated cobalt diselenide composite material through calcination. The method comprises the following steps of carrying out hydrothermal reaction on liquid acrylonitrile oligomer in situ polymerization to form a nitrogen-doped carbon precursor with a coating structure, and calcining the nitrogen-doped carbon precursor at high temperature to form the nitrogen-doped porous carbon material with a graphene-like structure. Compared with an amorphous carbon material, the graphene-like structure has excellent performances of good conductivity, high tensile strength and the like, in-situ polymerization can completely coat cobalt diselenide particles, and a two-dimensional lamellar structure can form a more complete conductive network.
It is noted that the liquid acrylonitrile oligomer is a self-made liquid acrylonitrile oligomer which is liquid at-80-200 ℃ because the polymer is a long chain macromolecule with high carbon content, which can provide a structural basis for the subsequent preparation of carbon coatings. The molecular weight of the liquid acrylonitrile oligomer is 100-100000. The acrylonitrile oligomer in the liquid acrylonitrile oligomer may be at least one of polypyrrole oligomer, polythiophene oligomer, polyaniline oligomer, polyacetylene oligomer, polystyrene oligomer, polycarbonate oligomer, polyamide resin oligomer, and the like, without being limited thereto.
According to the invention, acrylonitrile oligomer is adopted as a carbon source for in-situ polymerization, and finally the nitrogen-doped porous carbon material coated cobalt diselenide particles with the graphene-like structure are formed after calcination, so that the problems that the conventional carbon sources such as glucose and asphalt are not completely coated, the volume expansion problem is difficult to control, the conductive network is damaged due to particle pulverization and the like can be better solved. The nitrogen-doped porous carbon material with the graphene-like structure and the cobalt selenide particles are subjected to in-situ coating, so that the interface resistance can be reduced, the conductivity can be improved, the volume expansion can be limited, the rate capability and the cycle performance can be improved, and the purpose of improving the electrochemical performance can be achieved.
In step S1, preferably, the cobalt salt (e.g., Co (NO)3)2Etc. are not limited thereto) to selenium powder at a molar ratio of 1: 2.
Preferably, the first stirring time is 1-3h, such as 1h, 2h, 3 h.
In one embodiment, step S1 specifically includes: mixing Co (NO)3)2·6H2Dissolving O and selenium powder in methanol respectively, and magnetically stirring for 1-3h to obtain a cobalt salt methanol solution and a selenium powder methanol solution respectively.
In step S2, the second stirring time is preferably 1-3h, such as 1h, 2h, 3 h.
Preferably, the mass ratio of the added mass of the liquid acrylonitrile oligomer to the mass of the cobalt diselenide is 1-10: 1. The mass ratio can ensure enough carbon source, and a relatively complete graphene-like porous carbon material coating layer is prepared after reaction.
In one embodiment, step S2 specifically includes: quickly pouring the uniformly dispersed selenium powder methanol solution into Co (NO)3)2·6H2Adding 0.1-1g of liquid acrylonitrile oligomer into the O-methanol solution, continuously stirring for 1-3h until the methanol solution is uniformly dispersed, measuring 1-10mL of hydrazine hydrate solution (the mass concentration is 85%), and quickly adding the hydrazine hydrate solution into the uniformly dispersed methanol solution to obtain a mixed solution.
In step S3, the reaction temperature of the hydrothermal reaction is preferably 160 ℃ to 180 ℃, such as 160 ℃, 170 ℃, 180 ℃. The carbon source can be ensured to fully generate polymerization reaction within the temperature range, so that a relatively complete nitrogen-doped carbon precursor is prepared.
Preferably, the reaction time of the hydrothermal reaction is 18-30h, such as 18h, 19h, 30 h.
In one embodiment, step S3 specifically includes: and after the mixed solution is cooled, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 140 ℃ and 200 ℃ for 18-30h, cooling to room temperature, then carrying out centrifugal collection on the precipitate, and drying to obtain the precipitate.
In step S4, the calcination temperature is preferably 500-800 ℃. The full carbonization reaction of the nitrogen-doped carbon precursor can be ensured within the temperature range, and the porous carbon material coating layer with the graphene-like structure and high crystallinity and conductivity is prepared after the reaction.
Preferably, the temperature is raised to 500-800 ℃ at a temperature raising rate of 3-8 ℃/min.
Preferably, the calcination time is 4 to 6 hours.
In one embodiment, step S4 specifically includes: and raising the temperature of the precipitate to 800 ℃ at the heating rate of 3-8 ℃/min, preserving the heat for 4-6h, cooling, and grinding and sieving to obtain the nitrogen-doped porous carbon-coated cobalt diselenide composite material.
In a second aspect of the invention, the invention provides an application of the composite material of the invention, in particular, the composite material prepared by the method of the invention is used as a lithium ion battery cathode material.
Compared with the prior art, the invention has the beneficial effects that:
1) the liquid acrylonitrile oligomer (molecular weight of 100-100000) can realize in-situ polymerization coating of cobalt diselenide particles on a molecular level, and can release nitrogen to form a microporous structure in a high-temperature calcination process.
2) The cobalt diselenide particles can be well and uniformly coated and dispersed in the nitrogen-doped porous carbon coated structure, and the formed nitrogen-doped porous carbon coated support structure can limit the volume expansion of the cobalt diselenide particles, so that the circulation stability of the cobalt diselenide particles is remarkably improved.
3) The nitrogen-doped porous carbon-coated cobalt diselenide composite material prepared by the invention can effectively reduce the interface resistance, enhance the conductivity and improve the rate capability of the composite material. The composite material has lower production cost, simple and convenient method and much higher capacity than the graphite carbon material which is commercially applied at present, and the composite material has average specific discharge capacities of 875.1, 791.3, 697.8, 497.2, 343.6, 376.2 and 679.3mAh/g under current densities of 0.2A/g, 0.5A/g, 1A/g, 2A/g, 5A/g, 3A/g and 0.5A/g. The composite material prepared in the embodiment 1 of the invention still has the specific discharge capacity of 644mAh/g after 300 cycles under the flow density of 0.2A/g. Has good application prospect in the aspect of lithium ion battery cathode materials.
Drawings
FIG. 1 is a flow chart of a process for preparing a material obtained in comparative example and example 1;
FIG. 2 is an X-ray diffraction chart of the materials obtained in comparative example and example 1;
FIG. 3 is a photograph of a scanning electron microscope showing the materials obtained in comparative example and example 1;
FIG. 4 is a thermogravimetric analysis plot obtained in example 1;
FIG. 5 is a photograph of a transmission electron microscope showing the materials obtained in comparative example and example 1;
FIG. 6 is a plot of specific surface area versus void fraction analysis of the material obtained in example 1;
FIG. 7 is a graph showing the rate capability test of the materials obtained in comparative example and example 1;
FIG. 8 is a graph showing the cycle characteristics of the materials obtained in comparative example, example 1 and example 3;
FIG. 9 is a graph showing the AC impedance test of the materials obtained in comparative example and example 1.
Detailed Description
The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.
Example 1
A preparation method and application of a nitrogen-doped porous carbon-coated cobalt diselenide cathode material comprise the following steps:
mixing Co (NO)3)2·6H2Dissolving O (0.291g) and selenium powder (0.157g) in methanol respectively, magnetically stirring for 2 hr, and rapidly pouring the uniformly dispersed methanol solution of selenium powder into Co (NO)3)2·6H2Adding 0.5g of liquid acrylonitrile oligomer into the O-methanol solution, continuously stirring for 2 hours until the methanol solution is uniformly dispersed, measuring 5mL of hydrazine hydrate solution (the mass fraction is 85%), quickly adding the hydrazine hydrate solution into the uniformly dispersed methanol solution, transferring the solution into a hydrothermal reaction kettle after the solution is cooled, carrying out hydrothermal reaction at 180 ℃ for 24 hours, cooling to room temperature, collecting precipitate by centrifugation, drying, heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 4 hours for removing residual selenium powder. And after cooling, grinding and sieving to obtain the nitrogen-doped carbon-coated cobalt diselenide composite material.
Example 2
Mixing Co (NO)3)2·6H2O (0.268g) and selenium powder (B)0.144g) are respectively dissolved in methanol, the mixture is magnetically stirred for 1 hour, and the uniformly dispersed selenium powder methanol solution is quickly poured into Co (NO)3)2·6H2Adding 1g of liquid acrylonitrile oligomer into the O-methanol solution, continuously stirring for 1h until the methanol solution is uniformly dispersed, measuring 5mL of hydrazine hydrate solution (the mass fraction is 85%), quickly adding the hydrazine hydrate solution into the uniformly dispersed methanol solution, transferring the solution into a hydrothermal reaction kettle after the solution is cooled, carrying out hydrothermal reaction at 160 ℃ for 30h, cooling to room temperature, collecting precipitate by centrifugation, drying, heating to 800 ℃ at the heating rate of 8 ℃/min, and keeping the temperature for 4h to remove residual selenium powder. And after cooling, grinding and sieving to obtain the nitrogen-doped carbon-coated cobalt diselenide composite material.
Example 3
Mixing Co (NO)3)2·6H2Dissolving O (0.268g) and selenium powder (0.144g) in methanol respectively, magnetically stirring for 3h, and rapidly pouring the uniformly dispersed methanol solution of the selenium powder into Co (NO)3)2·6H2Adding 0.8g of liquid acrylonitrile oligomer into the O-methanol solution, continuously stirring for 3 hours until the methanol solution is uniformly dispersed, measuring 8mL of hydrazine hydrate solution (the mass fraction is 85%), quickly adding the hydrazine hydrate solution into the uniformly dispersed methanol solution, transferring the solution into a hydrothermal reaction kettle after the solution is cooled, carrying out hydrothermal reaction at 170 ℃ for 26 hours, cooling to room temperature, collecting precipitates by centrifugation, drying, heating to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 5 hours for removing residual selenium powder. And after cooling, grinding and sieving to obtain the nitrogen-doped carbon-coated cobalt diselenide composite material.
Comparative example 1
Mixing Co (NO)3)2·6H2Dissolving O (0.268g) and selenium powder (0.144g) in methanol respectively, magnetically stirring for 2h, and rapidly pouring the uniformly dispersed methanol solution of the selenium powder into Co (NO)3)2·6H2Continuously stirring for 2h in O-methanol solution until the methanol solution is uniformly dispersed, measuring 5mL of hydrazine hydrate solution (85%), quickly adding into the uniformly dispersed methanol solution, cooling the solution, reacting at 180 ℃ for 24h in a hydrothermal reaction kettle, cooling to room temperature, drying, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h,used for removing residual selenium powder. Cooling and collecting to obtain CoSe2Solid particles.
FIG. 1 is a flow chart of a process for producing a material obtained in comparative example and example 1. In order to test that the composite material provided by the invention has energy storage characteristics and can be used as a lithium battery cathode material, tests such as X-ray diffraction, a scanning electron microscope, a thermogravimetric analysis curve, a transmission electron microscope, an absorption and desorption curve of the composite material, a multiplying power performance of the composite material, a cycle performance of the composite material, an alternating current impedance spectrogram of the composite material and the like are carried out on the materials obtained in the examples and the comparative examples, and the test results are shown in fig. 2 to 9.
Specifically, fig. 2 is an X-ray diffraction pattern of the composite material obtained in example 1, and it can be seen from the X-ray diffraction pattern that the composite material contains a composite phase of cobalt diselenide and a carbon material, and diffraction peaks of the prepared composite material coincide with diffraction peaks of corresponding (211), (210) and (311) crystal planes of cobalt diselenide. Fig. 3 is a scanning electron microscope photograph of the materials obtained in comparative example and example 1, fig. 3(a) and 3(b) are the morphological characterization of the sample prepared in comparative example, fig. 3(a) shows that the prepared cobalt diselenide particles are composed of irregularly shaped nano-scale particles, and fig. 3(b) shows that the material has a nano-size particle structure. Fig. 3(c) and 3(d) are the morphology characterization of the composite material sample prepared in example 1, fig. 3(c) is the scanning electron microscope photograph of the composite material obtained in example 1, and it can be seen from fig. 3(c) and 3(d) that the cobalt diselenide particles are uniformly dispersed in the nitrogen-doped carbon-coated composite material, and this composite structure is beneficial to limiting the volume expansion of cobalt diselenide and can also enhance the conductivity of the composite material. FIG. 4 is a thermogravimetric analysis plot of the materials obtained in comparative example and example 1. From the figure, it can be obtained that the mass content of nitrogen-doped carbon in the composite material is 10.73%. FIG. 5 is a TEM photograph of the material obtained in comparative example and example 1. The comparison example is obviously different from the example 1 in the morphological characteristics, and the transmission electron microscope picture of the example 1 can obviously observe that the cobalt diselenide particles are dispersed in the nitrogen-doped carbon layer and are uniformly distributed; the structure of the amorphous carbon layer and the crystal lattice fringes of the cobalt diselenide particles can be obviously seen in a high-magnification transmission electron microscope photograph, and the distance between the structures and the crystal lattice fringes is measured and calculated to be 0.239nm of the crystal face of the cobalt diselenide particles (211). FIG. 6 is a plot of specific surface area versus void fraction analysis of the material obtained in example 1; fig. 6 demonstrates that the composite material contains a microporous structure, and the preparation method can form a microporous-structured composite material. FIG. 7 is a graph showing the rate capability test of the materials obtained in comparative example and example 1; the composite material of example 1 has average specific discharge capacities of 875.1, 791.3, 697.8, 497.2, 343.6, 376.2 and 679.3mAh/g at current densities of 0.2A/g, 0.5A/g, 1A/g, 2A/g, 5A/g, 3A/g and 0.5A/g, respectively. FIG. 8 is a graph showing the cycle characteristics of the materials obtained in comparative example, example 1 and example 3; the composite material prepared in the embodiment 1 still has a specific discharge capacity of 644mAh/g after 300 times of circulation under the current density of 0.2A/g, and the first coulombic efficiency reaches 78.7%. FIG. 9 is a graph showing the AC impedance test of the materials obtained in comparative example and example 1. In example 1, the interface resistance was reduced from 210.3 Ω to 80.4 Ω as compared with the control. The method can obviously reduce the interface resistance and improve the conductivity of the material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a nitrogen-doped porous carbon-coated cobalt diselenide composite material is characterized by comprising the following steps:
respectively dissolving cobalt salt and selenium powder in a solvent, and stirring for the first time to respectively obtain a cobalt salt solution and a selenium powder solution;
pouring the selenium powder solution into the cobalt salt solution, adding the liquid acrylonitrile oligomer, stirring for the second time, and adding the hydrazine hydrate solution after stirring to obtain a mixed solution;
transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction, and then cooling, centrifuging and drying to obtain a precipitate;
and calcining the precipitate, cooling, grinding and sieving to obtain the nitrogen-doped porous carbon-coated cobalt diselenide composite material.
2. The method for preparing the nitrogen-doped porous carbon-coated cobalt diselenide composite material according to claim 1, wherein the molar ratio of the cobalt salt to the selenium powder is 1: 2.
3. The method for preparing a nitrogen-doped porous carbon-coated cobalt diselenide composite material according to claim 1, wherein the first stirring time is 1-3 hours.
4. The method of claim 1, wherein the second stirring is performed for a period of 1-3 hours.
5. The method of claim 1, wherein the mass ratio of the added mass of the liquid acrylonitrile oligomer to the mass of the cobalt diselenide is 1-10: 1.
6. The method as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 160-180 ℃.
7. The method for preparing the nitrogen-doped porous carbon-coated cobalt diselenide composite material according to claim 1, wherein the reaction time of the hydrothermal reaction is 18-30 h.
8. The method as claimed in claim 1, wherein the calcination temperature is 500-800 ℃, and the calcination time is 4-6 h.
9. The method for preparing nitrogen-doped porous carbon-coated cobalt diselenide composite material as claimed in claim 8, wherein the temperature is raised to 500-800 ℃ at a temperature rise rate of 3-8 ℃/min.
10. The composite material prepared by the method of any one of claims 1 to 9 is used as a negative electrode material of a lithium ion battery.
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| CN115810492A (en) * | 2022-11-24 | 2023-03-17 | 福州大学 | Molybdenum diselenide-cobalt diselenide/nitrogen-doped graphene aerogel composite material and preparation method and application thereof |
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