CN109449411B - Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain - Google Patents

Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain Download PDF

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CN109449411B
CN109449411B CN201811280608.9A CN201811280608A CN109449411B CN 109449411 B CN109449411 B CN 109449411B CN 201811280608 A CN201811280608 A CN 201811280608A CN 109449411 B CN109449411 B CN 109449411B
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sodium tungstate
tungstate dihydrate
composite material
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CN109449411A (en
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黄剑锋
罗晓敏
曹丽云
李嘉胤
席乔
郭玲
王泽坤
王芳敏
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Adding sodium tungstate dihydrate into deionized water, stirring until the sodium tungstate dihydrate is dissolved to form a solution A, then adding glucose and PVP (polyvinyl pyrrolidone), uniformly mixing, adjusting the pH value to be 1.3-1.7, carrying out hydrothermal reaction at the temperature of 150-180 ℃ for 12-24 h, washing, and drying to obtain WO3@ C powder; mixing WO3Mixing @ C and thiourea, and calcining in argon atmosphere to obtain WS2@ C composite material. WS prepared according to the invention2The @ C composite material has simple process equipment and better product dispersibility, and the hydrothermal method is utilized to mix WO in a liquid phase3The material is uniformly compounded with the glucose carbon material which grows in situ, and the shape is controllable; then low-temperature calcination and vulcanization are utilized to quickly prepare WS2@ C composite material. WS prepared by the method2The @ C composite material has wide research value and application value in the electrochemical field.

Description

Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain
Technical Field
The present invention relates to WS2The technical field of nano material preparation relates to a method for synthesizing a cathode material in a limited domain by utilizing a hydrothermal method and low-temperature calcination, in particular to a method for synthesizing a tungsten disulfide @ C composite electrode material in a limited domain.
Background
Sodium ion batteries of transition metal chalcogenides (TMDs) widely studied as advanced energy storage materialsOne of the cell cathode materials, e.g. WS2，Sb2S3，GeS2，VS2And the like. At present, according to the reported literature, pure phase WS can be prepared by hydrothermal method, solid phase sintering method, chemical vapor deposition method and the like2A material. But due to WS2The material has poor crystallinity, unstable crystal structure, high capacity fading speed caused by easy amorphization in the charge and discharge processes and poor cycle stability, so that the material cannot be widely applied in practice.
At present, the traditional method for improving the electrochemical performance of the material comprises the steps of (1) constructing a nano-sized structure, reducing the size of the material, not only effectively relieving the volume expansion of the material, but also introducing huge specific surface area and providing a large number of interface active sites for the storage of ions. (2) To improve WS2The conductive particles of (2) can be compounded with a carbon material having a good conductivity. For example, Guowei Huang et al compounds tungsten disulfide with graphene oxide in three dimensions (Huang G, Liu H, Wang S, et al, hierarchical architecture of WS2nanosheets on graphene frames with enhanced electrochemical properties for lithium storage and hydrogen evolution [ J]Journal of Materials Chemistry A,2015,3(47): 24128-24138) as the negative electrode material of the lithium ion battery, the electrochemical performance of the tungsten disulfide after being compounded is greatly improved, the tungsten disulfide is cycled for 100 circles under the current density of 100mA/g, and the capacity of the tungsten disulfide is kept at 766 mAh/g. The compound material of tungsten disulfide and three-dimensional single-walled carbon nanotube is used as the cathode material of lithium ion battery (Ren J, Wang Z, Yang F, et al free and 3D single-walled carbon nanotubes/WS)2,nanosheets foams as ultra-long-life anodes for rechargeable lithium ion batteries[J]Electrochimica acta,2018.), greatly improves the cycling stability of the material, the material circulates for 1000 circles under the current density of 1A/g, and the capacity is stabilized at 688.9 mAh/g.
However, when the material is used for constructing a nano structure, the synthesis technology of the material is limited: the liquid phase condition is harsh, the requirements on temperature and time are strict, and the influence on the product is large; the solid phase condition synthesis is easy to agglomerate. Meanwhile, in the composite structure, the morphology is difficult to control.
Disclosure of Invention
The invention aims to provide a method for synthesizing a tungsten disulfide @ C composite electrode material in a limited domain manner, wherein WO is firstly fixed by carbon coating by utilizing the limited domain synthesis3Then vulcanized to achieve the purpose of controlling and compounding the shape and obtain WS2The @ C composite product has good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing a tungsten disulfide @ C composite electrode material in a limited domain mode comprises the following steps:
the method comprises the following steps: adding sodium tungstate dihydrate into deionized water, stirring until the sodium tungstate dihydrate is dissolved to form a solution A, then adding glucose and PVP, uniformly mixing, adjusting the pH value to 1.3-1.7, carrying out hydrothermal reaction at 150-180 ℃ for 12-24 h, washing, and drying to obtain WO3@ C powder;
step two: according to the molar ratio of 1 (10-30), adding WO3Mixing @ C and thiourea, and calcining in argon atmosphere to obtain WS2@ C composite material.
The further improvement of the invention is that the ratio of sodium tungstate dihydrate to deionized water is 0.618-1.65 g: 25 mL.
The invention is further improved in that the mass ratio of sodium tungstate dihydrate to glucose is 0.618-1.65: 0.168-0.45 g, and the mass ratio of the sodium tungstate dihydrate to the PVP is 10 (1-3).
The invention has the further improvement that the stirring speed is 400-600 r/min, and the stirring time is 0.1-1 h.
The invention is further improved in that 1-4 mol/L hydrochloric acid is adopted to adjust the pH value to 1.3-1.7.
The further improvement of the invention is that the calcining temperature is 700-900 ℃ and the time is 1-3 h.
A further improvement of the invention is that the calcination is carried out in a low temperature tube furnace. Compared with the prior art, the invention has the following beneficial effects:
the invention provides a concept of limited domain synthesis, and WO is firstly fixed by using carbon coating3And then the vulcanization is carried out in a limited area, so as to achieve the purposes of shape control and compounding. The invention isPrepared WS2The @ C composite material utilizes carbon to wrap tungsten disulfide, prevents the direct contact of electrolyte and tungsten disulfide, thereby the side reaction that tungsten disulfide and electrolyte brought has been reduced, polysulfide's production and its "shuttle effect" at electrochemical reaction in-process promptly, the coulomb efficiency of material in the charge-discharge process has been improved, utilize carbon cladding tungsten disulfide, can restrain its volume expansion that brings at the charge-discharge in-process, the stability of holding structure, thereby promote the circulation stability of material. The innovation of the invention is that carbon is coated on the tungsten trioxide material, and then the tungsten trioxide material is further vulcanized to obtain WS2The reason why @ C composite materials are often limited in their synthesis techniques when building nanostructures: the liquid phase condition is harsh, the requirements on temperature and time are strict, and the influence on the product is large; the solid phase condition is utilized for synthesis, which is easy to agglomerate, and simultaneously, the shape is difficult to control in the synthesis of a composite structure. Therefore, carbon is firstly coated on the tungsten trioxide material, the technological parameters are easy to control and repeat, and the tungsten trioxide material is further vulcanized to obtain WS2@ C composite material. The method has the advantages that glucose and PVP are used as carbon sources, raw materials are easy to obtain, the price is low, no pollution is generated, the green and scientific idea is met, and the PVP is used as a surfactant in the reaction process, so that the size of the material is effectively controlled. WS prepared according to the invention2The @ C composite material has simple process equipment and better product dispersibility, and the hydrothermal method is utilized to mix WO in a liquid phase3The material is uniformly compounded with the glucose carbon material which grows in situ, and the shape is controllable; then low-temperature calcination and vulcanization are utilized to quickly prepare WS2@ C composite material. WS prepared by the method2The @ C composite material has wide research value and application value in the electrochemical field.
Drawings
FIG. 1 shows WS prepared in example 32The X-ray diffraction (XRD) pattern of the @ C composite;
FIG. 2 shows WS prepared in example 32Scanning Electron Microscope (SEM) photographs of the @ C composite;
FIG. 3 is an enlarged view of a portion of FIG. 2;
FIG. 4 shows WS prepared in example 32Transmission Electron Microscope (TEM) photographs of @ C composite materials;
FIG. 5 is an enlarged view of a portion of FIG. 4; (ii) a
FIG. 6 shows WS prepared in example 32Graph of the cycling performance of @ C composite.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
The invention comprises the following steps:
the method comprises the following steps: under the condition of room temperature, 0.618-1.65 g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate dihydrate is completely dissolved to form a solution A, the stirring speed is 400-600 r/min, and the stirring time is 0.1-1 h;
step two: adding 0.168-0.45 g of glucose into the solution A, adding PVP, and controlling the molar ratio of the tungsten source to the carbon source to be 1:0.5, wherein m isGlucose：mPVPStirring until the glucose and the PVP are completely dissolved at a speed of 500r/min for 30min, wherein the ratio of glucose to PVP is 10: 1;
step three: diluting concentrated hydrochloric acid into a transparent solution B with the concentration of 1-4 mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.3-1.7, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 150-180 ℃ for 12-24 h, and naturally cooling to room temperature after the reaction is finished.
Step four: 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, placing the product in a freeze dryer with the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for drying for 8-12 hours to obtain black WO3@ C composite material.
Step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1 (10-30), enabling the tungsten source to be 0.1-0.5 g, enabling the calcination temperature to be 700-900 ℃, and enabling the heat preservation time to be 1-3 hours to obtain WS2@ C composite material.
Example 1
The method comprises the following steps: under the condition of room temperature, 0.618g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate is completely dissolved to form a solution A, the stirring speed is 600r/min, and the stirring time is 0.1 h;
step two: adding 0.168g of glucose and 0.0168g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 2mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.3, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 180 ℃ for 12h, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 20Pa for 8 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:20, taking the tungsten source as 0.1g, calcining at 900 ℃, and keeping the temperature for 2 hours to obtain WS2@ C composite material.
Example 2
The method comprises the following steps: under the condition of room temperature, 1.28g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate dihydrate is completely dissolved to form a solution A, the stirring speed is 600r/min, and the stirring time is 0.1 h;
step two: adding 0.349g of glucose and 0.0349g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 4mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is about 1.7, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 150 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, and taking out the productWashing with anhydrous ethanol and deionized water, centrifuging, washing for 5 times, drying in a freeze drier at-50 deg.C and vacuum degree of 40Pa for 8 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:15, taking the tungsten source as 0.2g, calcining at 700 ℃, and keeping the temperature for 3 hours to obtain WS2@ C composite material.
Example 3
The method comprises the following steps: under the condition of room temperature, 0.825g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate dihydrate is completely dissolved to form a solution A, the stirring speed is 600r/min, and the stirring time is 1 h;
step two: adding 0.225g of glucose and 0.0225g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 2mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.5, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 180 ℃ for 12h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, repeatedly washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 10Pa for 8 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:20, taking the tungsten source as 0.2g, calcining at 900 ℃, and keeping the temperature for 2 hours to obtain WS2@ C composite material.
Referring to FIG. 1, the samples were analyzed by a Japanese science D/max2000 PCX-ray diffractometer and found to be associated with WS of hexagonal system having JCPDS number 08-02372The structures are consistent, which shows that the method canPreparation of phase-pure WS2. The sample was observed with a Field Emission Scanning Electron Microscope (FESEM), and referring to FIGS. 2 and 3, it can be seen that WS was prepared2The product is coated by carbon material, and the coating amount is moderate without carbon spheres. The sample was observed with a transmission electron microscope, and referring to FIGS. 4 and 5, it can be seen that the WS was uniformly coated with the carbon material2The surface of the material.
The composite material is used as the negative electrode material of the sodium ion battery to carry out charge and discharge tests, and the current density is 100mA g as shown in figure 6-1The composite material shows better circulation stability at 100mA g-1After the material is charged and discharged for 80 circles under the current density, the capacity retention rate is 74%, the carbon coating effectively reduces the side reaction in the charging and discharging process, and the coulomb efficiency of the material is effectively improved.
Example 4
The method comprises the following steps: under the condition of room temperature, 1.65g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate dihydrate is completely dissolved to form a solution A, the stirring speed is 600r/min, and the stirring time is 0.1 h;
step two: adding 0.45g of glucose and 0.045g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 3mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.4, transferring the solution to a poly 100mL tetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 180 ℃ for 16h, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-50 deg.C and vacuum degree of 30Pa for 11 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The @ C powder is taken as a tungsten source, thiourea is taken as a sulfur source, the molar ratio of the tungsten source to the sulfur source is 1:20 under the protection of argon atmosphere in a low-temperature tube furnace, the tungsten source dosage is 0.5g, and the calcination temperature is 0.5gKeeping the temperature at 800 ℃ for 3h to obtain WS2@ C composite material.
Example 5
The method comprises the following steps: under the condition of room temperature, 0.711g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate is completely dissolved to form a solution A, the stirring speed is 600r/min, and the stirring time is 0.1 h;
step two: adding 0.194g of glucose and 0.0194g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 2mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.6, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 160 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 25Pa for 12 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:20, taking the tungsten source as 0.3g, calcining at 900 ℃, and keeping the temperature for 1h to obtain WS2@ C composite material.
Example 6
The method comprises the following steps: under the condition of room temperature, 0.711g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate is completely dissolved to form a solution A, the stirring speed is 400r/min, and the stirring time is 0.5 h;
step two: adding 0.194g of glucose and 0.0194g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B with the concentration of 1mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.6, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 170 ℃, the reaction time is 12 hours, and naturally cooling to the room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 25Pa for 12 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:30, taking the tungsten source as 0.3g, calcining at 700 ℃, and keeping the temperature for 3 hours to obtain WS2@ C composite material.
Example 7
The method comprises the following steps: under the condition of room temperature, 0.711g of sodium tungstate dihydrate is added into 25mL of deionized water and stirred until the sodium tungstate is completely dissolved to form a solution A, the stirring speed is 500r/min, and the stirring time is 0.4 h;
step two: adding 0.194g of glucose and 0.0194g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the molar ratio of the tungsten source to the carbon source to be 1: 0.5. Stirring at 500r/min for 30 min;
step three: diluting concentrated hydrochloric acid into a transparent solution B of 2mol/L, dropwise adding the solution B into the solution A until the pH value of the solution is 1.6, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 160 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 25Pa for 12 hr to obtain black WO3@ C composite material;
step five: subjecting the obtained WO3The preparation method comprises the following steps of using @ C powder as a tungsten source, using thiourea as a sulfur source, under the protection of argon atmosphere in a low-temperature tube furnace, enabling the molar ratio of the tungsten source to the sulfur source to be 1:20, taking the tungsten source as 0.3g, calcining at 800 ℃, and keeping the temperature for 1h to obtain WS2@ C composite material.
The invention provides a concept of limited domain synthesis, and WO is firstly fixed by using carbon coating3Then performing limited vulcanization to achieve the purpose of controlling and compounding the shape and obtain WS2@ C complex product.

Claims (5)

1. A method for synthesizing a tungsten disulfide @ C composite electrode material in a limited domain mode is characterized by comprising the following steps:
the method comprises the following steps: adding sodium tungstate dihydrate into deionized water, stirring until the sodium tungstate dihydrate is dissolved to form a solution A, then adding glucose and PVP, uniformly mixing, adjusting the pH value to 1.3-1.7, carrying out hydrothermal reaction at 150-180 ℃ for 12-24 h, washing, and drying to obtain WO3@ C powder; wherein the ratio of sodium tungstate dihydrate to deionized water is 0.618-1.65 g: 25mL, wherein the mass ratio of sodium tungstate dihydrate to glucose is (0.618-1.65): 0.168-0.45 g, wherein the mass ratio of sodium tungstate dihydrate to PVP is 10 (1-3);
step two: according to the molar ratio of 1 (10-30), adding WO3Mixing @ C and thiourea, and calcining in argon atmosphere to obtain WS2@ C composite material.
2. The method for synthesizing the tungsten disulfide @ C composite electrode material in a limited domain manner according to claim 1, wherein the stirring speed is 400-600 r/min, and the stirring time is 0.1-1 h.
3. The method for limited-domain synthesis of the tungsten disulfide @ C composite electrode material as claimed in claim 1, wherein 1-4 mol/L hydrochloric acid is used for adjusting the pH value to 1.3-1.7.
4. The method for limited-domain synthesis of the tungsten disulfide @ C composite electrode material as claimed in claim 1, wherein the calcining temperature is 700-900 ℃ and the calcining time is 1-3 h.
5. The method for regionally synthesizing the tungsten disulfide @ C composite electrode material according to claim 1, wherein the calcination is carried out in a low-temperature tube furnace.
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