CN109309224B - Preparation method of tungsten disulfide/CFC @ C multiphase composite electrode material - Google Patents

Preparation method of tungsten disulfide/CFC @ C multiphase composite electrode material Download PDF

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CN109309224B
CN109309224B CN201811279165.1A CN201811279165A CN109309224B CN 109309224 B CN109309224 B CN 109309224B CN 201811279165 A CN201811279165 A CN 201811279165A CN 109309224 B CN109309224 B CN 109309224B
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carbon cloth
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tungsten disulfide
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黄剑锋
罗晓敏
曹丽云
李嘉胤
王蓉
徐培光
席乔
王芳敏
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Shaanxi University of Science and Technology
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Abstract

A process for preparing the W disulfide/CFC @ C multiphase composite electrode material includes such steps as adding W hexachloride to alcohol, stirring, adding thioacetamide to obtain mixed solution, adding activated carbon cloth to said mixed solution, and homogeneous reaction to obtain WS2a/CFC composite; adding maltose and PVP into deionized water, and uniformly stirring to obtain a transparent solution; let WS be2Putting the/CFC composite material into a transparent solution, and carrying out homogeneous reaction after ultrasonic treatment to obtain the tungsten disulfide/CFC @ C multiphase composite electrode material. According to the invention, tungsten disulfide is coated again after growing on the carbon cloth substrate, so that the problem of volume expansion of the tungsten disulfide used as the cathode material of the sodium ion battery in the charging and discharging processes is solved, the structural stability of the tungsten disulfide is improved, and the electrochemical stability of the battery is improved. The invention prepares the multiphase composite material by a hydrothermal method, and has the advantages of simple preparation process, low raw material cost, easily controlled reaction temperature and short used time.

Description

Preparation method of tungsten disulfide/CFC @ C multiphase composite electrode material
Technical Field
The present invention relates to WS2The technical field of nano material preparation, in particular to a preparation method of a tungsten disulfide/CFC @ C multiphase composite electrode material.
Background
Transition metal chalcogenide, especially group VI transition metal sulfide of W, is a hot material of recent academic research due to its two-dimensional ordered layered structure and unique physicochemical functional properties. The structure is similar to graphene, and transition metal chalcogenides are combined together through strong inner layer covalent M-S bonds and weak van der Waals force interlayer interaction. The anisotropic laminated structure has excellent optical, electronic and mechanical properties, so that the anisotropic laminated structure is widely applied to the fields of biomedicine, energy storage, mechanical lubrication, catalysis, sensors, photoelectric devices and the like.
The preparation method comprises the following steps: hydrothermal method, Jingren et al reported that WS was synthesized in one step by hydrothermal method using sodium tungstate dihydrate as tungsten source and thiourea as sulfur source2And their complex products (Ren J, Wang Z, Yang F, et al free interpretation 3D single-wall carbon nanotubes/WS)2,nanosheets foams as ultra-long-life anodes for rechargeable lithium ion batteries[J]Electrochimica acta, 2018), but the synthesis temperature is higher, at 250 ℃. Tungsten disulfide has fast capacity attenuation and poor cycle stability due to larger volume expansion in the charging and discharging processes, and one method for solving the problem of collective expansion at present is to compound tungsten disulfide and a high-conductivity carbon material so as to relieve the structural damage caused in the volume expansion process and improve the capacity reduction. However, the recombination often cannot prevent the tungsten disulfide from directly contacting with the electrolyte during the charging and discharging processes, so that the side reaction is caused.
Disclosure of Invention
The invention aims to provide a preparation method of a tungsten disulfide/CFC @ C multiphase composite electrode material, which is characterized in that tungsten disulfide and carbon cloth are compounded and then coated again to form the multiphase composite electrode material, so that the problem of volume expansion of the electrode material as a sodium ion battery cathode material in the charging and discharging processes is solved, the carbon coating is utilized to prevent the tungsten disulfide from directly contacting with electrolyte, and the generation of side reactions in the charging and discharging processes is effectively relieved, so that the coulombic efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a tungsten disulfide/CFC @ C multiphase composite electrode material comprises the following steps:
the method comprises the following steps: adding tungsten hexachloride into ethanol, stirring until the tungsten hexachloride is dissolved to form a yellow clear solution, then adding thioacetamide, uniformly mixing to obtain a mixed solution, putting the activated carbon cloth into the mixed solution, after ultrasonic oscillation, carrying out homogeneous reaction at 200-220 ℃ for 4-48 h, cleaning the carbon cloth, and drying to obtain WS2a/CFC composite;
adding maltose and PVP into deionized water, and uniformly stirring to obtain a transparent solution;
step two: let WS be2Putting the/CFC composite material into a transparent solution, carrying out a homogeneous reaction for 12-24 h at 120-180 ℃ after ultrasonic treatment, cleaning carbon cloth, and drying to obtain the tungsten disulfide/CFC @ C multiphase composite electrode material.
The invention has the further improvement that the stirring speed is 600-1000 r/min, and the stirring time is 5-15 min.
The invention is further improved in that the concentration of the yellow clear solution is 0.025-0.1 mol/L.
The invention has the further improvement that the power of the ultrasound in the first step and the second step is 300-1000W, and the time is 5-15 min.
The invention further improves that the mass ratio of the tungsten hexachloride to the maltose to the PVP is (20-30): (1-3): (1-3).
The further improvement of the invention is that the ratio of maltose to deionized water is (0.2975 g-2.38): 30-60 mL.
The further improvement of the invention is that the specific process of the carbon cloth activation is as follows: cutting the carbon cloth into squares with the size of 3cm multiplied by 3cm, soaking the squares in nitric acid for 0.5-3h, repeatedly washing the squares with deionized water and ethanol until the squares are neutral, and drying the squares.
The invention is further improved in that the molar ratio of the tungsten hexachloride to the thioacetamide is (7-10) to (1-2).
Compared with the prior art, the invention has the following beneficial effects: the invention utilizes a hydrothermal method to prepare WS2the/CFC @ C multiphase composite material has the advantages of simple preparation process, low raw material cost, easily controlled reaction temperature and short used time. Firstly, after growing tungsten disulfide on a carbon cloth substrate, coating the carbon cloth substrate again, so that the problem of volume expansion of the carbon cloth substrate as a sodium ion battery cathode material in the charging and discharging processes is solved, the structural stability of the carbon cloth substrate is improved, and the electrochemical stability of the battery is improved; secondly, the carbon cloth is used as a matrix to grow the tungsten disulfide, so that the conductivity of the material is improved, and the transmission of electrons is facilitated; finally, the direct contact between the tungsten disulfide and the electrolyte is prevented by utilizing carbon coating, the generation of side reactions in the charging and discharging process is effectively relieved, the coulombic efficiency is effectively improved, and the carbon-coated tungsten disulfide electrolyte 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/CFC @ C heterogeneous composite;
FIG. 2 shows WS prepared in example 32X-ray diffraction (SEM) picture of/CFC composite material;
FIG. 3 shows WS prepared in example 32Scanning Electron Microscope (SEM) picture of/CFC @ C multiphase composite.
FIG. 4 shows WS prepared in example 32Scanning electron microscope (TEM) picture of/CFC @ C multiphase composite.
FIG. 5 shows WS prepared in example 32The circulating performance diagram of the/CFC @ C multiphase composite material is that the current density is 100mAg-1。
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings
The invention comprises the following steps:
the method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 0.5 to 3 hours for activation treatment, repeatedly washing the activated carbon cloth with deionized water and ethanol until the carbon cloth is neutral, and putting the carbon cloth into an oven with the temperature of 40 to 80 ℃ for drying for 4 to 12 hours for standby;
step two: adding tungsten hexachloride into 30-60 mL of ethanol solution, and magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution A, wherein the stirring speed is 600-1000 r/min, and the stirring time is 5-15 min. Controlling the concentration of the solution to be 0.025-0.1 mol/L;
step three: adding thioacetamide into the solution A, controlling n (WCl6): n (CH)3CSNH2) Stirring for 0.5-3h for (7-10): 1-2 to form a uniform mixed solution;
step four: putting the activated carbon cloth into the solution, putting the activated carbon cloth into an ultrasonic cleaner with the power of 300-1000W, and oscillating for 5-15 min;
step five: and (3) transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 200-220 ℃ for 4-48 h, and naturally cooling to room temperature after the reaction is finished.
Step six: and opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol, shaking for 5-15 min in an ultrasonic cleaner with the power of 300-1000W, repeatedly washing with deionized water and absolute ethyl alcohol, and then putting the carbon cloth into a vacuum drying oven to be dried for 4-8 h at the temperature of 40-70 ℃ to obtain the WS2/CFC composite material.
Step seven: taking a certain amount of maltose and PVP, putting into 30-60 mL of deionized water, and controlling the mass ratio m (WCl6) to m (maltose): m (PVP) and (1-3) respectively (20-30) and (1-3), magnetically stirring for 10-30 min at a rotation speed of 300-800 r/min to obtain a transparent solution;
step eight: let WS be2And putting the/CFC composite material into the transparent solution, putting the solution into an ultrasonic cleaner with the rate of 300-1000W, oscillating for 5-15 min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction, wherein the reaction temperature is 120-180 ℃, the reaction time is 12-24 h, and naturally cooling the solution to room temperature after the reaction is finished.
Step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 300-1000W, oscillating for 5-15 min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 4-8 h at the temperature of 40-70 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
Example 1
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, soaking the squares in concentrated nitric acid solution for 1h for activation treatment, repeatedly washing the activated carbon cloth with deionized water and ethanol until the carbon cloth is neutral, and drying the carbon cloth in an oven at 60 ℃ for 8h for later use;
step two: 0.2975g of tungsten hexachloride is added into 30mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 600r/min, and the stirring time is 10 min. Controlling the concentration of the solution to be 0.025 mol/L;
step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h at a ratio of 10:1 to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing into an ultrasonic cleaner with power of 500W, and shaking for 8 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous 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 six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 800W, oscillating for 10min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 4h at the temperature of 60 ℃ to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30mL of deionized water, and controlling the mass ratio m (WCl)6) M (maltose): m (PVP) 25:1:2, magnetically stirring for 15min at the rotating speed of 500r/min to obtain a transparent solution;
step eight: let WS be2The CFC composite material is put into the above-mentionedPutting the solution into an ultrasonic cleaner with the rate of 500W, shaking for 10min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 120 ℃, the reaction time is 12h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 500W, oscillating for 8min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 6h at 40 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
Example 2
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, soaking the squares in concentrated nitric acid solution for 3h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and then drying the carbon cloth in an oven at 60 ℃ for 8h for later use;
step two: 0.5625g of tungsten hexachloride is added into 45mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 600r/min, and the stirring time is 10 min. Controlling the concentration of the solution to be 0.0315 mol/L;
step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h at 4:1 to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing into an ultrasonic cleaner with power of 500W, and shaking for 8 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 4 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 800W, oscillating for 5min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 6h at the temperature of 60 ℃ to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30-60 mL of deionized water, and controlling the qualityBim (WCl)6) M (maltose): m (PVP) 25:2:1, magnetically stirring for 30min at the rotating speed of 700r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the rate of 300-1000W, oscillating for 10min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 160 ℃, the reaction time is 18h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 800W, oscillating for 15min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 5h at 70 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
Example 3
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 0.5h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and then putting the carbon cloth into a 60 ℃ oven for drying for 8h for later use;
step two: 1.386g of tungsten hexachloride is added into 50mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 600r/min, and the stirring time is 10 min. Controlling the concentration of the solution to be 0.07 mol/L;
step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing into an ultrasonic cleaner with power of 500W, and shaking for 8 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 210 ℃, the reaction time is 4 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol, oscillating the carbon cloth in an ultrasonic cleaner with the power of 300-1000W for 10min, and reacting the carbon cloth with deionized water and absolute ethyl alcoholAfter the secondary washing, the obtained product is put into a vacuum drying oven to be dried for 6 hours at 70 ℃ to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30-60 mL of deionized water, and controlling the mass ratio m (WCl)6) M (maltose): m (pvp) ═ 10: 1: 1, magnetically stirring for 25min at the rotating speed of 300r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the rate of 600W, shaking for 15min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 180 ℃, the reaction time is 12h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 1000W, oscillating for 5min, washing with deionized water and repeatedly washing with the absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying at 50 ℃ for 8h to obtain WS2a/CFC @ C heterogeneous composite.
Analysis of the samples with a Japanese science D/max2000 PCX-ray diffractometer (WS)2/CFC @ C multiphase composite), see fig. 1, sample was found to be associated with WS of hexagonal system having JCPDS numbers 08-02372The structures are consistent, which indicates that the product prepared by the method is pure phase. Observing the product with a Field Emission Scanning Electron Microscope (FESEM), FIG. 2 is WS2SEM picture of/CFC composite product shows that the prepared tungsten disulfide has good dispersibility, uniformly grows on carbon cloth and has no agglomeration phenomenon.
FIG. 3 shows WS2SEM picture of/CFC @ C multiphase composite material, WS can be seen2the/CFC composite is coated with a carbon layer.
FIG. 4 shows WS2TEM picture of/CFC @ C multiphase composite material shows that the WS is uniformly coated with the carbon layer2The carbon layer on the/CFC composite material has a thickness of about 30-80 nm.
Referring to FIG. 5, it is used as a sodium ion battery material at 100mA g-1The capacity of the capacitor is hardly reduced and is kept at 450mAh g by circulating for 20 circles under the current density of (1)-1And its coulombic efficiency is maintained at 99%The 'shuttle effect' of polysulfide is effectively inhibited by the bright carbon coating, and the cycling stability of the material is effectively improved.
Example 4
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 2.5h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and then putting the carbon cloth into a 60 ℃ oven for drying for 8h for later use;
step two: 2.38g of tungsten hexachloride is added into 60mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 600r/min, and the stirring time is 10 min. Controlling the concentration of the solution to be 0.1 mol/L;
step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h at a ratio of 10:1 to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing into an ultrasonic cleaner with power of 500W, and shaking for 8 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 48 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 300-1000W, oscillating for 12min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, and drying the carbon cloth in a vacuum drying oven at 60 ℃ for 5h to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30-60 mL of deionized water, and controlling the mass ratio m (WCl)6) M (maltose): m (PVP) 20:2:3, magnetically stirring for 30min at the rotating speed of 500r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the placing rate of 700W, shaking for 5min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction, wherein the reaction temperature is 160 ℃, the reaction time is 10h, and after the reaction is finished, the CFC composite material is placed into the transparent solutionNaturally cooling to room temperature;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 300-1000W, oscillating for 8min, washing the carbon cloth with deionized water and absolute ethyl alcohol, and drying the carbon cloth in a vacuum drying oven at 65 ℃ for 7h to obtain WS2a/CFC @ C heterogeneous composite.
Example 5
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 2h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and putting the carbon cloth into a 60 ℃ oven for drying for 8h for later use;
step two: 0.4528g of tungsten hexachloride is added into 40mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 600r/min, and the stirring time is 10 min. Controlling the concentration of the solution to be 0.0285 mol/L;
step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing into an ultrasonic cleaner with power of 500W, and shaking for 8 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 600W, oscillating for 10min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 6h at the temperature of 50 ℃ to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30-60 mL of deionized water, and controlling the mass ratio m (WCl)6) M (maltose): m (PVP) 15:2:3, magnetically stirring for 10-30 min at the rotating speed of 300-800 r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the placing rate of 300W, shaking for 12min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction, wherein the reaction temperature is 150 ℃, the reaction time is 16h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 600W, oscillating for 10min, washing with deionized water and repeatedly washing with the absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying for 6h at 55 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
Example 6
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 2h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and putting the carbon cloth into a 60 ℃ oven for drying for 8h for later use;
step two: 0.4528g of tungsten hexachloride is added into 40mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 1000r/min, and the stirring time is 5 min.
Step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h at 8:1.5 to form a uniform mixed solution;
step four: putting the activated carbon cloth into the solution, putting the solution into an ultrasonic cleaner with the power of 300W, and oscillating for 15 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 210 ℃, the reaction time is 4 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 600W, oscillating for 10min, repeatedly washing the carbon cloth with deionized water and absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying the carbon cloth for 6h at the temperature of 50 ℃ to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, and putting 30-60 mL of deionized waterIn water, mass ratio m (WCl) is controlled6) M (maltose): m (PVP) 30:1:3, magnetically stirring for 10-30 min at the rotating speed of 300r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the placing rate of 300W, shaking for 12min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction, wherein the reaction temperature is 130 ℃, the reaction time is 24h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 600W, oscillating for 10min, washing with deionized water and repeatedly washing with the absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying for 6h at 55 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
Example 7
The method comprises the following steps: cutting carbon cloth (CFC) into squares with the size of 3cm multiplied by 3cm, putting the squares into concentrated nitric acid solution for soaking for 2h for activation treatment, repeatedly washing the activated carbon cloth to be neutral by deionized water and absolute ethyl alcohol, and putting the carbon cloth into a 60 ℃ oven for drying for 8h for later use;
step two: 0.4528g of tungsten hexachloride is added into 40mL of ethanol solution and stirred magnetically until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 700r/min, and the stirring time is 15 min.
Step three: thioacetamide is added into the solution A, and the molar ratio n (WCl6) to n (CH) is controlled3CSNH2) Stirring for 2h at a ratio of 5:1 to form a uniform mixed solution;
step four: placing the activated carbon cloth into the solution, placing the solution into an ultrasonic cleaner with the power of 1000W, and oscillating for 5 min;
step five: transferring the solution and the carbon cloth to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 48 hours, and naturally cooling to room temperature after the reaction is finished;
step six: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 1000W, shaking for 5min, repeatedly washing with deionized water and absolute ethyl alcohol,drying in a vacuum drying oven at 50 deg.C for 6 hr to obtain WS2a/CFC composite;
step seven: taking a certain amount of maltose and PVP, putting into 30mL of deionized water, and controlling the mass ratio m (WCl)6) M (maltose): m (PVP) 20:3:1, stirring for 10min by magnetic force at the rotating speed of 300r/min to obtain a transparent solution;
step eight: let WS be2Placing the/CFC composite material into the transparent solution, placing the solution into an ultrasonic cleaner with the placing rate of 1000W, shaking for 5min, transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction, wherein the reaction temperature is 170 ℃, the reaction time is 12h, and naturally cooling the solution to room temperature after the reaction is finished;
step nine: opening the reaction kettle, taking out the carbon cloth, putting the carbon cloth into 30mL of absolute ethyl alcohol in an ultrasonic cleaner with the power of 600W, oscillating for 10min, washing with deionized water and repeatedly washing with the absolute ethyl alcohol, putting the carbon cloth into a vacuum drying oven, and drying for 6h at 55 ℃ to obtain WS2a/CFC @ C heterogeneous composite.
The present invention prepares WS by means of solution heat and hydrothermal process2a/CFC @ C heterogeneous composite. The experimental operation process is simple, the raw material cost is low, the reaction temperature is easy to control, and the used time is short. The carbon cloth is used as the substrate to grow the tungsten disulfide, so that the conductivity of the material is improved, the transmission of electrons is facilitated, and the carbon cloth has wide research value and application value in the electrochemical field.

Claims (6)

1. A preparation method of a tungsten disulfide/CFC @ C multiphase composite electrode material is characterized by comprising the following steps:
the method comprises the following steps: adding tungsten hexachloride into ethanol, stirring until the tungsten hexachloride is dissolved to form a yellow clear solution, then adding thioacetamide, uniformly mixing to obtain a mixed solution, putting the activated carbon cloth into the mixed solution, carrying out ultrasonic oscillation, carrying out homogeneous reaction at 200-220 ℃ for 4-48 h, and then carrying out homogeneous reactionCleaning and drying the carbon cloth to obtain WS2a/CFC composite;
adding maltose and PVP into deionized water, and uniformly stirring to obtain a transparent solution; the mass ratio of the tungsten hexachloride to the maltose to the PVP is (20-30): (1-3): (1-3); the molar ratio of the tungsten hexachloride to the thioacetamide is (7-10) to (1-2);
step two: let WS be2Putting the/CFC composite material into a transparent solution, carrying out a homogeneous reaction for 12-24 h at 120-180 ℃ after ultrasonic treatment, cleaning carbon cloth, and drying to obtain the tungsten disulfide/CFC @ C multiphase composite electrode material.
2. The preparation method of the tungsten disulfide/CFC @ C multiphase composite electrode material as claimed in claim 1, wherein the stirring speed is 600-1000 r/min, and the stirring time is 5-15 min.
3. The method for preparing the tungsten disulfide/CFC @ C multiphase composite electrode material according to claim 1, wherein the concentration of the yellow clear solution is 0.025-0.1 mol/L.
4. The preparation method of the tungsten disulfide/CFC @ C multiphase composite electrode material according to claim 1, wherein the power of ultrasound in the first step and the second step is 300-1000W, and the time is 5-15 min.
5. The method for preparing the tungsten disulfide/CFC @ C multiphase composite electrode material according to claim 1, wherein the ratio of maltose to deionized water is (0.2975 g-2.38 g): 30-60 mL.
6. The method for preparing the tungsten disulfide/CFC @ C multiphase composite electrode material according to claim 1, wherein the specific process of carbon cloth activation is as follows: cutting the carbon cloth into squares with the size of 3cm multiplied by 3cm, soaking the squares in nitric acid for 0.5-3h, repeatedly washing the squares with deionized water and ethanol until the squares are neutral, and drying the squares.
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