CN111874950B - Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof - Google Patents

Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof Download PDF

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CN111874950B
CN111874950B CN202010762965.XA CN202010762965A CN111874950B CN 111874950 B CN111874950 B CN 111874950B CN 202010762965 A CN202010762965 A CN 202010762965A CN 111874950 B CN111874950 B CN 111874950B
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graphene oxide
tungsten disulfide
electrode material
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黄剑锋
罗晓敏
曹丽云
李嘉胤
王瑜航
王羽偲嘉
王芳敏
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a vanadium-doped tungsten disulfide/graphene oxide composite electrode material and a preparation method and application thereof, and belongs to the technical field of tungsten disulfide nano material preparation. The preparation method provided by the invention utilizes a two-step hydrothermal method to prepare the vanadium-doped tungsten disulfide/graphene oxide composite electrode material: vanadium is fixed on a graphene oxide substrate by utilizing primary hydrothermal, and then tungsten disulfide nanosheets are grown by utilizing secondary hydrothermal. The preparation method has the advantages of simple operation, low raw material cost, easily controlled reaction temperature and short used time. According to the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the invention, the WS is inhibited by utilizing the larger specific surface area and the better flexibility of the graphene oxide 2 The agglomeration of the nano-sheets and the doping of vanadium provides active sites, so that the electrochemical performance of the material is improved, and the material has wide research value and application value in the electrochemical field.

Description

Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of tungsten disulfide nano materials, and relates to a vanadium-doped tungsten disulfide/graphene oxide composite electrode material as well as a preparation method and application thereof.
Background
Layered tungsten disulfide (WS) 2 ) The transition metal sulfide (TMD) is one of transition metal sulfides (TMD) which is discovered at the earliest and is researched more, has weak interlayer Van der Waals force shared by a TMD family, is easy to prepare into a single-layer or multi-layer nano sheet by peeling, and has wide application prospect in energy storage devices due to better stability and semiconductor characteristics of a nano structure. The layered structure of the TMD nano material is Li + The migration of ions in the charging and discharging process is facilitated, and MoS 2 And WS 2 As a representative of TMD materials, Li can be used as an electrode material of a lithium ion battery + Ions are relatively easily intercalated or deintercalated from the electrode material.
Although WS 2 Has larger specific surface area, but has lower electron mobility and can provide smaller capacitance, so the photoelectric property and the electrochemical property of the material are improved by compounding or element doping with other materials. The graphene oxide has larger specific surface area and better flexibility, and can be used as the growth WS 2 An ideal substrate for the nanoplatelets. The composite graphene oxide can effectively inhibit WS 2 The agglomeration among the nano sheets effectively improves the circulation stability of the nano sheets. However, tungsten disulfide itself belongs to a semiconductor material, and the conductivity of tungsten disulfide is poor, so that the problem of electrochemical reaction lag exists in the charge-discharge reaction process, and the rate capability of tungsten disulfide is poor. Therefore, the conductivity of the material can be improved and the active positioning points can be increased by doping the metal elements so as to improve the rate capability. At present, most doping methods mainly utilize chemical vapor deposition, and the synthesis temperature is generally higher, and the energy consumption is larger. And chemical vapor deposition is suitable for bulk materials, and the uniformity of the product is difficult to control. On the other hand, the potassium storage capacity of WS2 electrode has been studied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, and a preparation method and application thereof. The preparation method disclosed by the invention utilizes two hydrothermal reactions to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material. The experimental operation process is simple and easy to control, and the raw material cost is low; by the preparation method, the vanadium-doped tungsten disulfide/graphene oxide composite electrode material can be prepared in a large scale in a short time, and the vanadium-doped tungsten disulfide/graphene oxide composite electrode material is applied to a potassium ion battery cathode material to show excellent potassium storage performance, so that the vanadium-doped tungsten disulfide/graphene oxide composite electrode material has wide research value and application value in the electrochemical field.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, which comprises the following steps:
1) uniformly dispersing graphene oxide and sodium metavanadate in water to obtain a solution A; carrying out hydrothermal homogeneous reaction on the solution A, and cooling to obtain a product system A containing a vanadium simple substance graphene oxide matrix;
2) uniformly dispersing tungsten hexachloride and thioacetamide in a product system A to obtain a suspension B; carrying out hydrothermal reaction on the suspension B to grow tungsten disulfide nanosheets, and cooling to obtain a product system B; centrifugally washing the product system B, and then freeze-drying to collect powder to obtain the vanadium-doped tungsten disulfide/graphene oxide composite material;
3) And calcining and annealing the vanadium-doped tungsten disulfide/graphene oxide composite material to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material.
Preferably, in the step 1), the reaction charge ratio of the graphene oxide, the sodium metavanadate, the water, the tungsten hexachloride and the thioacetamide is (30-60) mg, (0.0073-0.073) g, (30-60) mL, (0.238-2.38) g and (0.45-4.5) g.
Preferably, in the step 1), the reaction temperature of the hydrothermal reaction is 180-220 ℃, and the reaction time is 12-36 h.
Preferably, in the step 2), the reaction temperature is 200-240 ℃ and the reaction time is 12-48 h.
Preferably, in the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 6 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
Preferably, the calcination annealing treatment in step 3) specifically includes: the calcination temperature is 500-800 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
The invention also discloses the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method.
Preferably, the capacity of the composite electrode material reaches 368mAh & g -1 (ii) a At 1 A.g -1 After the current density of (2) was cycled for 500 cycles, the capacity retention rate was 88.7%.
The invention also discloses application of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material as a battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, which comprises the steps of firstly fixing simple substance vanadium on a Graphene Oxide (GO) substrate by utilizing primary hydrothermal, and then growing tungsten disulfide (WS) on the GO substrate fixed with the simple substance vanadium by utilizing secondary hydrothermal 2 ) Nanosheet to obtain vanadium-doped tungsten disulfide/graphene oxide (WS) 2 /GO) composite electrode material. The invention prepares the vanadium-doped WS by a two-step hydrothermal method 2 the/GO composite electrode material is prepared into the nano-sized vanadium-doped tungsten disulfide/graphene oxide composite electrode material with uniform appearance without high-temperature treatment, and the preparation method has the advantages of simple and efficient preparation process, low raw material cost and easily-controlled reaction temperature.
The invention also discloses the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method. The composite electrode material utilizes the graphene oxide with larger specific surface area and better flexibility, and can effectively inhibit WS 2 The agglomeration among the nano sheets and the introduction of vanadium doping provide more active sites, so that the electrochemical performance of the material is greatly improved.
Furthermore, the cycle performance test proves that the capacity of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the invention can reach 368 mAh.g when the vanadium-doped tungsten disulfide/graphene oxide composite electrode material is activated by small current -1 Higher capacity is exhibited; at 1 A.g -1 After circulating for 500 cycles at a current density of 158mAh g -1 The capacity retention rate was 88.7%, showing excellent capacity retention rate performance.
The invention also discloses application of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material to a battery cathode material. Through relevant experimental detection, the vanadium-doped tungsten disulfide/graphene oxide composite electrode material shows excellent potassium storage performance, so that the vanadium-doped tungsten disulfide/graphene oxide composite electrode material has wide research value and application value in the electrochemical field.
Drawings
Fig. 1 is an X-ray diffraction pattern of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in example 3 of the present invention;
fig. 2 is a scanning electron microscope image of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in embodiment 3 of the present invention; wherein, (a) is a low-power graph and (b) is a high-power graph;
Fig. 3 is a transmission electron microscope image of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in embodiment 3 of the present invention;
fig. 4 is an energy spectrum of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in example 3 of the present invention; wherein, (a) is the shape of the selected area, (b) is C, W, S, V element distribution, (C) is C element, (d) is W element, (e) is S element, and (f) is V element;
fig. 5 is a cycle performance diagram of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material for a negative electrode material of a potassium ion battery, which is prepared in embodiment 3 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses vanadium-doped tungsten disulfide/graphene oxide (WS) 2 The preparation method of the/GO) composite electrode material comprises the following steps:
the method comprises the following steps: and adding 30-60 mg of GO into 30-60 mL of deionized water, and carrying out ultrasonic treatment for 6-12h to obtain a uniform brown solution A. Adding 0.0073-0.073 g of sodium metavanadate, and controlling the GO concentration to be 0.5-2 mg/ml.
Step two: and transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the temperature of 180-220 ℃ for 12-36 h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 0.238-2.38 g of tungsten hexachloride and 0.45-4.5 g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500-800 r/min, and the stirring time is 30-120 min.
Step four: and transferring the solution B into a homogeneous reactor to carry out secondary hydrothermal reaction at 200-240 ℃ for 12-48 h, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, and drying the product in a freeze dryer at the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for 6-12 hours.
Step six: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 500-800 ℃, the heat preservation time is 1-4 h, and the heating rate is 5-20 ℃/min. Obtaining vanadium doped WS 2 a/GO composite electrode material.
The present invention is described in further detail below with reference to specific examples:
example 1
The method comprises the following steps: 60mg of GO is added into 30mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.058g of sodium metavanadate is added, and the concentration of GO is controlled to be 2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 180 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.65g of tungsten hexachloride and 2.28g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500r/min, and the stirring time is 30 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 200 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4 times, and drying the product in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 10Pa for 6 hours. Obtaining vanadium doped WS 2 a/GO composite electrode material.
Example 2
The method comprises the following steps: 30mg of GO is added into 60mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.073g of sodium metavanadate is added, and the concentration of GO is controlled to be 0.5 mg/ml.
Step two: and transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at 220 ℃ for 36h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 0.238g of tungsten hexachloride and 0.45g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 800r/min, and the stirring time is 120 min.
Step four: and transferring the solution B into a homogeneous reactor to perform a secondary hydrothermal reaction at 240 ℃ for 48 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer with the temperature of-70 ℃ and the vacuum degree of 40Pa for 12 hours. Obtaining vanadium doped WS 2 a/GO composite electrode material.
Example 3
The method comprises the following steps: 60mg of GO is added into 60mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.045g of sodium metavanadate is added, and the concentration of GO is controlled to be 1 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 200 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.19g of tungsten hexachloride and 2.25g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 700r/min, and the stirring time is 60 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 200 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer with the temperature of-40 ℃ and the vacuum degree of 40Pa for 12 hours. Obtaining vanadium doped WS 2 a/GO composite electrode material.
Example 4
The method comprises the following steps: 45mg of GO is added into 45mL of deionized water, and the mixture is subjected to ultrasonic treatment for 10 hours to obtain a uniform brown solution A. 0.073g of sodium metavanadate was added, controlling the GO concentration to 1 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 200 ℃ for 36h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 2.38g of tungsten hexachloride and 4.45g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500r/min, and the stirring time is 75 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 220 ℃, the reaction time is 36 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer with the temperature of-60 ℃ and the vacuum degree of 30Pa for 8 hours. Obtaining vanadium doped WS 2 a/GO composite electrode material.
Example 5
The method comprises the following steps: 60mg of GO is added into 50mL of deionized water, and the mixture is subjected to ultrasonic treatment for 8 hours to obtain a uniform brown solution A. 0.0098g of sodium metavanadate is added, and the concentration of GO is controlled to be 1.2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 180 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 2.07g of tungsten hexachloride and 3.68g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 600r/min, and the stirring time is 45 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 210 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step five: opening reactionAnd (3) taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, carrying out centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer at the temperature of-50 ℃ and the vacuum degree of 35Pa for 8 hours. Obtaining vanadium doped WS 2 a/GO composite electrode material.
Example 6
The method comprises the following steps: 60mg of GO is added into 50mL of deionized water, and the mixture is subjected to ultrasonic treatment for 8 hours to obtain a uniform brown solution A. 0.0073g of sodium metavanadate is added, and the concentration of GO is controlled to be 1.2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.65g of tungsten hexachloride and 4.5g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 600r/min, and the stirring time is 45 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 240 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer at the temperature of-50 ℃ and the vacuum degree of 40Pa for 6 hours. To obtain vanadium-doped WS 2 a/GO composite electrode material.
In conclusion, the invention utilizes a two-step hydrothermal method to obtain vanadium-doped WS 2 the/GO composite electrode material has the advantages of simple experimental operation process, low raw material cost, easy control of reaction temperature and short used time. GO is used as a substrate to grow tungsten disulfide nanosheets, and GO has a large specific surface area and good flexibility and can effectively inhibit WS 2 The agglomeration among the nano sheets effectively improves the circulation stability of the nano sheets. Doping vanadium into WS 2 the/GO composite material improves the conductivity of the material, increases the active positioning points and greatly improves the rate capability of the material.
The invention is described in further detail below with reference to the accompanying drawings:
see fig. 1 for exampleVanadium doped WS prepared in example 3 2 An X-ray diffraction (XRD) pattern of the/GO composite electrode material; sample and WS of hexagonal system having JCPDS number 08-0237 2 The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists.
FIG. 2 shows the vanadium doped WS prepared in example 3 2 Scanning Electron Microscope (SEM) pictures of the/GO composite electrode material. The tungsten disulfide nanosheets uniformly grow on the surface of the graphene oxide.
FIG. 3 shows the vanadium doped WS prepared in example 3 2 And (4) a Transmission Electron Microscope (TEM) picture of the/GO composite electrode material. The result is consistent with the scan result.
FIG. 4 shows the preparation of vanadium doped WS 2 The energy spectrum of the/GO composite electrode material can see that W, S, C, V and other elements are uniformly distributed, and the vanadium exists in a doped form by combining the fact that no obvious peak of vanadium or vanadium compounds exists in XRD.
FIG. 5 shows vanadium doped WS 2 the/GO composite material is used as a potassium ion battery cathode material and has the cycle performance under high current. It can be seen that the capacity of the catalyst can reach 368 mAh.g when the catalyst is activated by small current -1 Higher capacity is exhibited. After 1 A.g -1 After circulating for 500 cycles at a current density of 158mAh g -1 The capacity retention rate is 88.7%, and the excellent potassium storage performance is shown.
Analysis of the samples with a Japan science D/max2000 PCX-ray diffractometer (vanadium doped WS) 2 /GO composite) found with WS of hexagonal system with JCPDS numbers 08-0237 2 The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists. The sample is observed by a Field Emission Scanning Electron Microscope (FESEM) and a transmission electron microscope, and the tungsten disulfide nanosheet can be uniformly grown on the graphene oxide. And the prepared product has better dispersibility and uniform size distribution. The observed appearance and scanning of the transmission are consistent, and the uniform distribution of W, S, C, V elements and the like can be seen from the energy spectrum test, which indicates that the vanadium-doped WS is successfully synthesized 2 the/GO composite material is found to have the structure from the electrochemical performance test thereofExcellent potassium storage performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (9)

1. A preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material is characterized by comprising the following steps:
1) uniformly dispersing graphene oxide and sodium metavanadate in water to obtain a solution A; carrying out hydrothermal homogeneous reaction on the solution A, and cooling to obtain a product system A containing a vanadium simple substance graphene oxide matrix;
2) uniformly dispersing tungsten hexachloride and thioacetamide in a product system A to obtain a suspension B; carrying out hydrothermal reaction on the suspension B to grow tungsten disulfide nanosheets, and cooling to obtain a product system B; centrifugally washing the product system B, and then freeze-drying to collect powder to obtain the vanadium-doped tungsten disulfide/graphene oxide composite material;
3) and calcining and annealing the vanadium-doped tungsten disulfide/graphene oxide composite material to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material.
2. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the reaction charge ratio of graphene oxide, sodium metavanadate, water, tungsten hexachloride and thioacetamide is (30-60) mg, (0.0073-0.073) g, (30-60) mL, (0.238-2.38) g and (0.45-4.5) g.
3. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the reaction temperature of the hydrothermal reaction is 180-220 ℃, and the reaction time is 12-36 h.
4. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 2), the reaction temperature is 200-240 ℃ and the reaction time is 12-48 h.
5. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 6 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
6. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein the calcination annealing treatment in the step 3) specifically comprises: the calcination temperature is 500-800 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
7. The vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method of any one of claims 1 to 6.
8. The vanadium-doped tungsten disulfide/graphene oxide composite electrode material of claim 7, wherein the capacity of the composite electrode material reaches 368 mAh-g -1 (ii) a At 1 A.g -1 After the current density of (2) is cycled for 500 cycles, the capacity retention rate is 88.7%.
9. Use of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 7 or 8 as a battery negative electrode material.
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