CN113410439B - Vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material and preparation method and application thereof - Google Patents

Vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material and preparation method and application thereof Download PDF

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CN113410439B
CN113410439B CN202110529176.6A CN202110529176A CN113410439B CN 113410439 B CN113410439 B CN 113410439B CN 202110529176 A CN202110529176 A CN 202110529176A CN 113410439 B CN113410439 B CN 113410439B
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vanadium
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CN113410439A (en
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杨成浩
黄倩晖
吴理觉
汪华
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South China University of Technology SCUT
Guangdong Jiana Energy Technology Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
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Abstract

The invention discloses a vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material and a preparation method and application thereof; the material comprises trivanadium tetrasulfide and a nitrogen-doped carbon spherical core shell, wherein the trivanadium tetrasulfide is of a hollow sphere structure, and the surface of the trivanadium tetrasulfide is coated with the nitrogen-doped carbon spherical core shell. Adding a vanadium source, a carbon source and hydrogen peroxide into an alcohol solvent to carry out hydrothermal reaction to obtain a suspension A; centrifugally washing and drying the vanadium trioxide/carbon spherical core-shell structure material, and carrying out heat treatment in a reducing atmosphere to obtain a vanadium trioxide/carbon spherical core-shell structure material; and adding a sulfur source and a nitrogen source under a protective atmosphere, and carrying out heat treatment to obtain the vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material. The material obtained by the invention is used for the negative electrode of the potassium ion battery and shows excellent electrochemical performance. The method has strong operability and low cost, and solves the problem of poor circulation stability caused by large volume fluctuation of the transition metal sulfide in the circulation process in the prior art.

Description

Vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material and preparation method and application thereof
Technical Field
The invention belongs to the field of potassium ion battery cathode materials, and particularly relates to a trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material, and a preparation method and application thereof.
Background
Although lithium ion secondary batteries are widely used in various small portable devices and large-scale energy storage systems in power systems, their inherent scarcity and increasing lithium consumption limit their large-scale use in the future. In this regard, the abundant reserves of potassium on earth and electrochemical properties similar to lithium make potassium ion batteries promising candidates. Potassium ions have a lower reduction potential than sodium ions, while potassium ions have a weaker lewis acidity, making the solvated ions of potassium ions smaller than lithium and sodium ions, which gives potassium ion batteries a wider electrochemical voltage window and higher energy density.
Transition metal oxides, particularly vanadium oxides of different compositions, have received extensive attention from researchers due to their advantages of high theoretical capacity, low discharge potential, low cost, safety, environmental protection, and the like. But the inherently low electrical conductivity of the material prevents it from achieving energy storage requirements. Vanadium Sulfide (VS) in comparison with vanadium oxide 2 、V 2 S 3 、V 5 S 8 And V 3 S 4 ) Better conductivity and higher theoretical capacity. Moderate bonding between vanadium and sulfur can reduce electrode polarization, thereby improving energy efficiency, and reduce thermal effects due to weak bonding strength, and has been widely synthesized for use as an anode material of an alkali metal secondary battery. For example, vanadium disulfide (VS) 2 ) With multilayer nanoplatelets in which an atomic layer of vanadium is sandwiched between two S layers, a graphite-like layered structure and a large interlayer spacing (0.576nm) can provide sufficient storage space for potassium ions with large ionic radii, but at large magnification, the layered stack structure limits rapid diffusion of stored electrons and ions in a two-dimensional plane. Vanadium trisulfide (V) 3 S 4 ) Usually from V 0.5 VS 2 Composition, with a unique twisted NiAs-type structure, VS 2 The single-layer structure and the additional V atom connecting the two adjacent layers improve the diffusion rate of electron/ion charge carriers, and have good application prospect when being used as a negative electrode material of alkali metal ions.
However, in practical applications, during repeated potassium removal/potassium removal of metal sulfides, the ion/electron transport kinetics is slow, the volume change is severe, the structure collapses, leading to severe pulverization and repeated formation of unstable Solid Electrolyte Interface (SEI) films, resulting in severe capacity fade and unsatisfactory rate performance. Carbon-based materials such as graphene oxide, carbon nanotubes or hollow carbon spheres are usually introduced to support vanadium trisulfide. However, these carbon materials are expensive, and their addition lowers the specific capacity of the entire electrode. Therefore, an efficient and reliable structural design is needed to solve the above problems.
For example: chinese patent document CN109148857A provides a preparation method and application of a sodium ion battery cathode material vanadium tetrasulfide/carbon nanotube, which comprises the following steps: s1, adding a vanadium source into water, heating and continuously stirring until the vanadium source is dissolved, adding a sulfur source, heating and continuously stirring until the vanadium source is dissolved, and obtaining a solution A; s2, adding the multi-walled carbon nano-tube into water, and carrying out ultrasonic treatment to obtain a suspension B; s3, adding the solution A into the suspension B, and continuously stirring to obtain a suspension C; and S4, heating the suspension C obtained in the step S3, carrying out hydrothermal reaction, centrifugally washing, and drying to obtain the cathode material vanadium tetrasulfide/carbon nano tube of the sodium-ion battery. But vanadium tetrasulfide does not bond well to carbon nanotubes as seen by scanning electron microscopy. The material has poor cycle stability when used for testing electrochemical performance, and the current density is 0.1A g -1 The capacity after 30 circles of lower circulation is only 187.9mAh/g, and the capacity retention rate is only 62.3%.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention successfully solves the problems by adopting structural design and constructing the carbon coating layer in a synergistic manner, and provides the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
The trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material comprises trivanadium tetrasulfide and nitrogen-doped carbon spherical core-shell, wherein the trivanadium tetrasulfide is of a hollow sphere structure, and the surface of the trivanadium tetrasulfide is coated with the nitrogen-doped carbon spherical core-shell.
The preparation method of the carbon spherical core-shell structure material doped with vanadium tetrasulfide/nitrogen comprises the following steps:
(1) adding a vanadium source, a carbon source and hydrogen peroxide into an alcohol solvent to carry out hydrothermal reaction to obtain a suspension A;
(2) centrifugally washing and drying the suspension A in the step (1), and carrying out heat treatment in a reducing atmosphere to obtain a vanadium trioxide/carbon spherical core-shell structure material;
(3) and (3) adding a sulfur source and a nitrogen source into the vanadium trioxide/carbon spherical core-shell structure material obtained in the step (2) under a protective atmosphere, and carrying out heat treatment to obtain the vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material.
Preferably, the vanadium source added in the step (1) is one of vanadium acetylacetonate, vanadium pentoxide, ammonium metavanadate, triisopropoxyl vanadium oxide, vanadyl sulfate and vanadyl trichloride; further preferred are vanadyl acetylacetonate;
preferably, the carbon source is one of a sugar or an organic acid; more preferably, the saccharide is glucose, sucrose, maltose, trehalose, xylose; the organic acid is tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, salicylic acid, and benzoic acid.
Preferably, the alcohol solvent is one of methanol, ethanol, propanol, ethylene glycol or glycerol;
preferably, the mass concentration of the hydrogen peroxide is controlled to be 6-12%;
preferably, the volume ratio of the hydrogen peroxide to the alcohol solvent is 1/6-1/2;
preferably, the molar ratio of vanadium element in the vanadium source to carbon element in the carbon source is controlled to be 1: 1-30; further preferably, the molar ratio of vanadium element in the vanadium source to carbon element in the carbon source is controlled to be 1: 3-5, the carbon shell of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material obtained in the ratio is moderate in thickness, and the electrochemical performance is optimal;
preferably, the temperature of the hydrothermal reaction in the step (1) is 120-200 ℃, and the time of the hydrothermal reaction is 18-30 h.
Preferably, the temperature of the heat treatment in the step (2) is 500-700 ℃, and the time is 3-5 h.
Preferably, the reducing atmosphere in the step (2) is nitrogen/hydrogen mixed gas or argon/hydrogen mixed gas, wherein the proportion of nitrogen or argon is 0-95%; further preferably, the proportion of nitrogen or argon is 90%.
Preferably, the protective atmosphere in step (3) is a nitrogen/hydrogen gas mixture or an argon/hydrogen gas mixture, wherein the proportion of nitrogen or argon is 0-95%. More preferably, the proportion of nitrogen or argon is 70% to 95%.
Preferably, the sulfur source in step (3) is one of sulfur powder, thioacetamide and thiourea;
preferably, the mass ratio of the vanadium trioxide/carbon spherical core-shell structure material to the sulfur source in the step (3) is 1: 10-30; sulfur source at high temperature and H 2 Generation of H 2 S, in H 2 Under the atmosphere of S, vanadium trioxide can be sulfurized into vanadium tetrasulfide;
preferably, the mass ratio of the vanadium trioxide/carbon spherical core-shell structure material to the nitrogen source in the step (3) is 1: 1-20; as a nitrogen doping agent, the nitrogen source can be decomposed at high temperature to generate ammonia gas, and nitrogen-doped carbon can be formed in the ammonia gas atmosphere to provide more active sites for potassium deposition;
preferably, the nitrogen source in step (3) is urea.
Preferably, the temperature of the heat treatment in the step (3) is 400-600 ℃, and the time is 1-3 h.
The vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material is applied as a potassium ion battery cathode material.
The invention provides a preparation method of a vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material.
A vanadium source and a carbon source are added into an alcohol solvent, hydrogen peroxide is added to play a role in regulating and controlling morphology, a carbon-coated vanadium trioxide hollow sphere precursor is obtained through hydrothermal reaction, then the carbon-coated vanadium trioxide hollow sphere precursor is vulcanized, nitrogen is doped into a carbon shell in the vulcanization process, and finally the vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material is obtained and used for a potassium ion battery cathode to show excellent electrochemical performance. The method has strong operability and low cost, and solves the problem of poor circulation stability caused by large volume fluctuation of the transition metal sulfide in the circulation process in the prior art.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) firstly, the nitrogen doped carbon coating has the following functions:
1) the low intrinsic conductivity of vanadium trisulfide is improved, and the rate capability of the battery is facilitated;
2) the contact of vanadium trisulfide particles is blocked, the dissolution of vanadium is effectively prevented from entering the electrolyte, and possible side reactions are reduced;
3) nitrogen doping provides more active sites for potassium ion de-intercalation, so that the reversible capacity of the battery is improved;
4) the carbon coating enhances the structural rigidity of the material, greatly relieves the problem of large volume expansion of the trivanadium tetrasulfide in the process of embedding/removing potassium ions, relieves the agglomeration of the trivanadium tetrasulfide and is beneficial to the cycling stability of the battery;
(2) secondly, the hollow structure can effectively buffer the volume change in the charging and discharging process, and meanwhile, the electrolyte penetration can be optimized, the ion diffusion distance can be shortened, and the rate capability of the battery can be enhanced;
the unique structure avoids direct contact between vanadium trisulfide particles and electrolyte, inhibits side reaction to a certain extent, and in addition, carbon-coated vanadium trisulfide can prevent particle agglomeration and structural collapse, and improves the conductivity of the material.
Drawings
FIG. 1 is a scanning electron microscope image of the intermediate vanadium trioxide/carbon composite material obtained in example 1;
FIG. 2 is a scanning electron microscope of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material obtained in example 1;
FIG. 3 is a graph of rate capability of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material obtained in example 1;
FIG. 4 is a graph of the cycle performance of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material obtained in example 1.
Detailed Description
The technical solution of the present invention is described below clearly and completely with reference to the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
0.1856g of vanadyl acetylacetonate and 0.69g of glucose are accurately weighed and dissolved into 30mL of anhydrous methanol together, magnetic stirring is carried out at room temperature, 5mL of hydrogen peroxide solution (prepared by mixing 1mL of 40% concentration analytically pure hydrogen peroxide and 4mL of deionized water) is added, stirring is carried out for 1h, and then the mixture is transferred into a 50mL hydrothermal kettle and undergoes hydrothermal reaction at 150 ℃ for 24 h. The resulting product was washed several times with anhydrous ethanol by centrifugation, and then dried overnight in an air-blown dry oven at 60 ℃. Placing the collected powder into a ceramic burning boat, and performing Ar/H 2 Under mixed gas (Ar: H) 2 95: 5) carrying out heat treatment at 600 ℃ for 4h to obtain a vanadium trioxide/carbon composite material; then placing the obtained vanadium trioxide/carbon composite material into a ceramic burning boat and placing the ceramic burning boat in the middle section of a tubular furnace, placing 3g of sublimed sulfur powder and 2g of urea at the air inlet end of the tubular furnace, and then placing the sublimed sulfur powder and the urea in Ar/H 2 (Ar：H 2 95: 5) and (3) carrying out heat treatment for 1h at 500 ℃ under the mixed gas to obtain the vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material.
Fig. 1 is a scanning electron micrograph of the intermediate vanadium trioxide/carbon composite material obtained in this example, and it can be seen from the micrograph that the intermediate product has a uniform spherical structure, a smooth surface, and a size of about 1 μm. Fig. 2 is a scanning electron micrograph of the final product obtained in this example, which shows that the final product still has a uniform spherical structure after vulcanization, and the surface of the final product is rougher than that of vanadium trioxide.
Weighing 0.4g of the prepared vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material, 0.05g of acetylene black (conductive agent) and 0.05g of CMC (binding agent), adding a proper amount of deionized water for dispersion, fully mixing and pulping for 6h, uniformly coating on a copper foil, drying overnight in an air-blast drying oven at 80 ℃, cutting into pieces, taking a potassium piece as a counter electrode and glass fiber as a diaphragm, and dropwise adding a proper amount of 0.8M KPF 6 DEC-1: 1 (volume ratio) electrolyte, formulated in a glove box as 2032 button cell.
FIG. 3 is a graph showing the rate capability of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material obtained in this example; the electrode material is 0.05, 0.1,0.2,0.5A g -1 Respectively exhibit 379.4, 292.4, 240.5 and 190.1mAh g -1 And at 0.5A g -1 180.8mAh g still remained after 40 cycles of circulation under the current density -1 Exhibits excellent rate capability;
fig. 4 is a cycle performance diagram of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material prepared in this example. The electrode material had a current density of 2A g -1 181.25mAh g can be kept after 300 cycles of lower circulation -1 The reversible capacity and the capacity retention rate of the vanadium tetrasulfide are 91.1%, which shows that the material prepared by the example well improves the cycle stability of the vanadium tetrasulfide material.
Example 2
0.1856g of vanadyl acetylacetonate and 0.69g of glucose are accurately weighed and dissolved into 30mL of anhydrous methanol together, magnetic stirring is carried out at room temperature, 5mL of hydrogen peroxide solution (prepared by mixing 1mL of 40% concentration analytically pure hydrogen peroxide and 4mL of deionized water) is added, stirring is carried out for 1h, and then the mixture is transferred into a 50mL hydrothermal kettle and undergoes hydrothermal reaction at 180 ℃ for 24 h. The resulting product was washed several times with anhydrous ethanol by centrifugation, and then dried overnight in an air-blown dry oven at 60 ℃. Placing the collected powder into a ceramic burning boat, and performing Ar/H 2 Mixed gas (Ar: H) 2 85: 15) carrying out heat treatment at 700 ℃ for 3h to obtain a vanadium trioxide/carbon composite material; then placing the obtained vanadium trioxide/carbon composite material into a ceramic burning boat and placing the ceramic burning boat in the middle section of a tubular furnace, placing 3g of sublimed sulfur powder and 2g of urea at the air inlet end of the tubular furnace, and then placing the sublimed sulfur powder and the urea in Ar/H 2 Under mixed gas (Ar: H) 2 85: 15) and performing heat treatment at 500 ℃ for 2h to obtain the vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material.
Example 3
0.1856g of vanadyl acetylacetonate and 0.69g of glucose are accurately weighed and dissolved into 30mL of anhydrous methanol together, magnetic stirring is carried out at room temperature, 5mL of hydrogen peroxide solution (prepared by mixing 1mL of 40% concentration analytically pure hydrogen peroxide and 4mL of deionized water) is added, stirring is carried out for 1h, and then the mixture is transferred into a 50mL hydrothermal kettle and undergoes hydrothermal reaction at 120 ℃ for 24 h. The resulting product was washed several times with anhydrous ethanol by centrifugation, and then dried overnight in an air-blown dry oven at 60 ℃. Placing the collected powder into a ceramic burning boat, and performing Ar/H 2 Under mixed gas (Ar: H) 2 80: 20) carrying out heat treatment at 500 ℃ for 4h to obtain a vanadium trioxide/carbon composite material; then placing the obtained vanadium trioxide/carbon composite material into a ceramic burning boat and placing the ceramic burning boat in the middle section of a tubular furnace, placing 3g of sublimed sulfur powder and 2g of urea at the air inlet end of the tubular furnace, and then placing the sublimed sulfur powder and the urea in Ar/H 2 Under mixed gas (Ar: H) 2 80: 20) and performing heat treatment at 600 ℃ for 1h to obtain the vanadium trisulfide/nitrogen-doped carbon spherical core-shell structure material.
Example 4
0.1856g of vanadyl acetylacetonate and 0.69g of glucose are accurately weighed and dissolved into 30mL of anhydrous methanol together, magnetic stirring is carried out at room temperature, 5mL of hydrogen peroxide solution (prepared by mixing 1mL of 40% concentration analytically pure hydrogen peroxide and 4mL of deionized water) is added, stirring is carried out for 1h, and then the mixture is transferred into a 50mL hydrothermal kettle and undergoes hydrothermal reaction at 150 ℃ for 18 h. The resulting product was washed several times with anhydrous ethanol by centrifugation, and then dried overnight in an air-blown dry oven at 60 ℃. Placing the collected powder into a ceramic burning boat at Ar/H 2 Under mixed gas (Ar: H) 2 80: 20) carrying out heat treatment at 600 ℃ for 4h to obtain a vanadium trioxide/carbon composite material; then putting the obtained vanadium trioxide/carbon composite material into a ceramic burning boat and puttingPlacing 3g of sublimed sulfur powder and 2g of urea at the gas inlet end of the tube furnace, and placing the sublimed sulfur powder and the urea at the Ar/H position 2 Under mixed gas (Ar: H) 2 80: 20) and performing heat treatment at 500 ℃ for 1h to obtain the vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (5)

1. The application of the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material as a potassium ion battery cathode material is characterized in that the trivanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material comprises trivanadium tetrasulfide and nitrogen-doped carbon spherical core-shell, the trivanadium tetrasulfide is of a hollow sphere structure, and the surface of the trivanadium tetrasulfide is coated with the nitrogen-doped carbon spherical core-shell;
the preparation method of the vanadium trisulfide/nitrogen doped carbon spherical core-shell structure material comprises the following steps:
(1) adding a vanadium source, a carbon source and hydrogen peroxide into an alcohol solvent to carry out hydrothermal reaction to obtain a suspension A; the temperature of the hydrothermal reaction is 120-200 ℃, and the time of the hydrothermal reaction is 18-30 h;
(2) centrifugally washing and drying the suspension A in the step (1), and carrying out heat treatment in a reducing atmosphere to obtain a vanadium trioxide/carbon spherical core-shell structure material; the temperature of the heat treatment is 500-700 ℃, and the time is 3-5 h;
(3) adding a sulfur source and a nitrogen source into the vanadium trioxide/carbon spherical core-shell structure material obtained in the step (2) under a protective atmosphere, and carrying out heat treatment to obtain vanadium tetrasulfide/nitrogen-doped carbon spherical core-shell structure material; the temperature of the heat treatment is 400-600 ℃, and the time is 1-3 h.
2. The use according to claim 1, wherein the vanadium source added in step (1) is one of vanadium acetylacetonate, vanadium pentoxide, ammonium metavanadate, triisopropoxytrianisum oxide, vanadyl sulfate and vanadyl trichloride; the carbon source is one of saccharides or organic acids; the alcohol solvent is one of methanol, ethanol, propanol, glycol or glycerol; the mass concentration of the hydrogen peroxide is controlled to be 6-12%; the volume ratio of the hydrogen peroxide to the alcohol solvent is 1/6-1/2; the molar ratio of vanadium element in the vanadium source to carbon element in the carbon source is controlled to be 1: 1-30.
3. Use according to claim 2, characterized in that the sugars are glucose, sucrose, maltose, trehalose, xylose; the organic acid is tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, salicylic acid, and benzoic acid.
4. The use of claim 1, wherein the reducing atmosphere in step (2) is a nitrogen/hydrogen mixture or an argon/hydrogen mixture, wherein the proportion of nitrogen or argon is 0-95%; the protective atmosphere in the step (3) is nitrogen/hydrogen mixed gas or argon/hydrogen mixed gas, wherein the proportion of nitrogen or argon is 0-95%.
5. The use according to claim 1, wherein the sulfur source in step (3) is one of sulfur powder, thioacetamide, thiourea; in the step (3), the mass ratio of the vanadium trioxide/carbon spherical core-shell structure material to the sulfur source is 1: 10-30, the mass ratio of the vanadium trioxide/carbon spherical core-shell structure material to the nitrogen source is 1: 1-20, and the nitrogen source is urea.
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