CN109449410B - Preparation method of nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material - Google Patents

Preparation method of nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material Download PDF

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CN109449410B
CN109449410B CN201811280597.4A CN201811280597A CN109449410B CN 109449410 B CN109449410 B CN 109449410B CN 201811280597 A CN201811280597 A CN 201811280597A CN 109449410 B CN109449410 B CN 109449410B
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sulfur
nitrogen
ion battery
sodium ion
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CN109449410A (en
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黄剑锋
罗晓敏
曹丽云
李嘉胤
王蓉
徐培光
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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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

Nitrogen and sulfur co-dopingAdding tungsten hexachloride into ethanol, magnetically stirring until the tungsten hexachloride is completely dissolved to form a clear solution, then adding thioacetamide, melamine and trithiocyanuric acid, and carrying out a homogeneous reaction for 4-48 h at 200-240 ℃ to obtain black powder; and calcining the black powder under the protection of argon atmosphere to obtain the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery cathode material. The invention successfully prepares the nitrogen and sulfur co-doped WS by using tungsten hexachloride, thioacetamide and carbon cloth as raw materials through methods of solvothermal and thermal treatment assisted by melamine and trithiocyanuric acid and the like2An electrode material. The invention has simple operation process and easily controlled reaction temperature. The nitrogen and sulfur co-doping provides more active sites for the electrode material, which is beneficial to the transmission of ions and electrons, thereby improving the electrochemical performance of the battery.

Description

Preparation method of nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material
Technical Field
The present invention relates to WS2The technical field of nano material preparation, in particular to a preparation method of a nitrogen and sulfur co-doped tungsten disulfide sodium ion battery cathode material.
Background
WS2The nano material has a unique two-dimensional nano structure, and the conventional flaky tungsten disulfide crystal is composed of a unit layer consisting of S ═ W ═ S. In the unit layer, each W atom is bonded to two S atoms by a strong covalent bond, and the atoms in the crystal form a network plane structure by arrangement, and are bonded between planes by weak van der Waals force. Insoluble in acid, alkali and alcohol, has certain reducibility, and can react with strong oxidizing substances such as aqua regia, nitric acid and hot concentrated sulfuric acid. Simultaneously has higher specific surface area, surface effect, quantum size effect and small size effect, and is widely applied to electrical materials and nano materialsThe sensor, the nano catalytic material, the nano lubricating material and other fields are one of popular novel functional materials researched abroad in recent years.
Tungsten disulfide is a good electrode material because of the unique layered structure and the larger interlayer spacing, is beneficial to the ion desorption of the battery in the electrochemical charge and discharge process, but the structural stability of the material is poor because the tungsten disulfide has poor conductivity and larger volume expansion in the charge and discharge process. According to the research progress at home and abroad, the carbon material is taken as the matrix, so that the electron transmission is facilitated, the volume expansion of tungsten disulfide in the charge and discharge process can be relieved, and the electrochemical performance of the composite material as the lithium ion battery cathode material is effectively improved. For example, Guowei Huang et al compounds tungsten disulfide with three-dimensional graphene oxide (Huang G, Liu H, Wang S, et al, hierarchical architecture of WS2 nanosheets on graphene frames with enhanced electrochemical properties for lithium ion battery anode Materials and hydrogen evolution [ J ]. Journal of Materials Chemistry A,2015,3(47): 24128) and uses it as lithium ion battery anode material, and the electrochemical performance of the tungsten disulfide after compounding is greatly improved, and the capacity is kept at 766mAh/G after 100mA/G circulation. However, the tungsten disulfide material has the problem of poor conductivity, the doping can often solve the problem, defects are introduced into the material, active sites contacted with electrolyte are effectively improved, the number of current carriers is controlled, the conductivity of the material is improved, the transmission of electrons is accelerated, and the electrochemical performance of the material is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: adding tungsten hexachloride into ethanol, magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution, then adding thioacetamide, melamine and trithiocyanuric acid, carrying out a homogeneous reaction at 200-220 ℃ for 4-48 h, washing, and drying to obtain black powder;
step two: and calcining the black powder under the protection of argon atmosphere to obtain the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery cathode material.
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 stirring speed is 600-1000 r/min, and the time is 5-15 min.
A further improvement of the invention is that the molar ratio of tungsten hexachloride to thioacetamide is 10: 1; the mass ratio of the tungsten hexachloride to the melamine to the trithiocyanuric acid is (7-10): (0.5-2): (0.5-2).
The further improvement of the invention is that the calcining temperature is 600-1000 ℃ and the time is 1-3 h.
A further development of the invention consists in 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 successfully prepares the nitrogen and sulfur co-doped WS by using tungsten hexachloride, thioacetamide and carbon cloth as raw materials through methods of solvothermal and thermal treatment assisted by melamine and trithiocyanuric acid and the like2An electrode material. The method has simple operation process and easily controlled reaction temperature, and can quickly prepare the high-purity nitrogen and sulfur co-doped WS2And (3) compounding a sodium storage electrode material. The nitrogen and sulfur co-doping provides more active sites for the electrode material, which is beneficial to the transmission of ions and electrons, thereby improving the electrochemical performance of the battery2The electrode material has wide research value and application value in the electrochemical field.
Drawings
FIG. 1 shows nitrogen and sulfur co-doped WS prepared in example 32An X-ray diffraction (XRD) pattern of the composite electrode material;
FIG. 2 shows the nitrogen and sulfur co-doped WS prepared in example 32Scanning electron microscope (SE) of composite electrode materialM) photograph.
FIG. 3 shows the nitrogen and sulfur co-doped WS prepared in example 32Cycle performance diagram of composite electrode material with current density of 100mA g-1。
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: 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 two: adding thioacetamide into the solution A, and controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) (7-10) in weight ratio (0.5-2): (0.5-2), stirring for 0.5-3h to form a uniform mixed solution;
step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the temperature of 200-220 ℃ for 4-48 h, and naturally cooling to room temperature after the reaction is finished.
Step four: 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 the product for 4 to 6 times, and drying the product in a freeze dryer at the temperature of between 40 ℃ below zero and 70 ℃ below zero for 8 to 12 hours under the vacuum degree of 10 to 40Pa to obtain black powder.
Step five: putting black powder into a magnetic boat, calcining at 600-1000 ℃ for 1-3 h under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 1
The method comprises the following steps: 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 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.025 mol/L;
step two: 0.5625g of thioacetamide is added to the solution A, the molar ratio n (n:)WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 0.5h at a ratio of 10:1:1 to form a uniform mixed solution;
step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 12h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 4 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 10Pa for 8 hours to obtain black powder.
Step five: putting the black powder into a magnetic boat, calcining for 1h at 600 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 2
The method comprises the following steps: 0.595g 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 800r/min, and the stirring time is 5 min. Controlling the concentration of the solution to be 0.0375 mol/L;
step two: to solution A was added 1.127g of thioacetamide, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 1.5h to form a uniform mixed solution, wherein the ratio of the mixed solution to the mixed solution is 7:0.5: 1;
step three: and transferring the solution 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 four: and opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 6 times, and drying in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 35Pa for 10 hours to obtain black powder.
Step five: putting the black powder into a magnetic boat, calcining for 2h at 700 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 3
The method comprises the following steps: 1.19g 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 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.05 mol/L;
step two: 2.25g thioacetamide was added to the solution A, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 3 hours to form a uniform mixed solution, wherein the ratio of the mixed solution to the mixed solution is 9:2: 1;
step three: and transferring the solution 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 four: and opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 5 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 60Pa for 12 hours to obtain black powder.
Step five: putting the black powder into a magnetic boat, calcining for 3h at 800 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Analysis of the samples with a Japan science D/max2000 PCX-ray diffractometer (Nitrogen, Sulfur Co-doped WS)2Electrode material), see fig. 1, the samples were found to be associated with WS of hexagonal system numbered 08-0237 for JCPDS2The structures are consistent, which indicates that the product prepared by the method is pure phase. The sample was observed with a Field Emission Scanning Electron Microscope (FESEM), and referring to FIG. 2, it can be seen that the prepared product was dispersedThe performance is better, the size distribution is uniform, and the nano-flake shape is presented.
Referring to fig. 3, it is used as the negative electrode material of sodium ion battery at 100mAg-1After circulating for 100 circles, 485mAh g remains in the capacity-1The better cycle stability can be seen in figure 3.
Example 4
The method comprises the following steps: 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 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.1 mol/L;
step two: 4.5g thioacetamide was added to the solution A, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 0.5h under the condition of 10:1.5:2 to form a uniform mixed solution;
step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 10 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 5 times, and drying in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 20Pa for 8 hours to obtain black powder.
Step five: putting the black powder into a magnetic boat, calcining for 1.5h at 1000 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 5
The method comprises the following steps: 1.037g of tungsten hexachloride is added into 40mL of ethanol solution and stirred by magnetic force until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.065 mol/L;
step two: 1.965g of thioacetamide are added to the solution A, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 3 hours to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous 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 four: opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 4 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 10Pa for 8 hours to obtain black powder;
step five: putting the black powder into a magnetic boat, calcining for 2h at 600 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 6
The method comprises the following steps: 1.037g of tungsten hexachloride is added into 40mL of ethanol solution and stirred by magnetic force until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.065 mol/L;
step two: 1.965g of thioacetamide are added to the solution A, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 3h under the condition of 10:2:0.5 to form a uniform mixed solution;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 48 hours, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 4 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 10Pa for 8 hours to obtain black powder;
step five: putting the black powder into a magnetic boat, calcining for 1h at 1000 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
Example 7
The method comprises the following steps: 1.037g of tungsten hexachloride is added into 40mL of ethanol solution and stirred by magnetic force until the tungsten hexachloride is completely dissolved to form yellow clear solution A, the stirring speed is 700r/min, and the stirring time is 8 min. Controlling the concentration of the solution to be 0.065 mol/L;
step two: 1.965g of thioacetamide are added to the solution A, controlling the molar ratio n: (WCl6):n(CH3CSNH2) Adding melamine and trithiocyanuric acid, and controlling mass ratio m (to) of (1 to 10)WCl6):m(C3H6N6):m(C3H3N3S3) Stirring for 3 hours to form a uniform mixed solution, wherein the ratio of the mixed solution to the mixed solution is 7:1: 2;
step three: transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 215 ℃, the reaction time is 30h, and naturally cooling to room temperature after the reaction is finished;
step four: opening the reaction kettle, taking out a product, sequentially washing by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation, repeatedly washing for 4 times, and drying in a freeze dryer at the temperature of-60 ℃ and the vacuum degree of 10Pa for 8 hours to obtain black powder;
step five: putting the black powder into a magnetic boat, calcining for 3h at 600 ℃ under the protection of argon atmosphere in a low-temperature tube furnace to obtain nitrogen and sulfur co-doped WS2An electrode material.
The method takes tungsten hexachloride as a tungsten source and thioacetamide as a sulfur source, and adopts a solvothermal method to obtain the nitrogen-sulfur co-doped WS2An electrode material. Simple preparation process, easily controlled process parameters, high repeatability, no need of large-scale expensive equipment for reaction, great saving of energy consumption and production cost, good product dispersibility, and rapid preparation of high-purity nitrogen and sulfur co-doped WS2The electrode material and nitrogen and sulfur co-doping provide more active sites for the electrode material, which is beneficial to the transmission of ions and electrons, thereby improving the electrochemical performance of the battery,nitrogen and sulfur co-doped WS prepared by using method2The electrode material has small size and high purity, and has wide research value and application value in the electrochemical field.

Claims (6)

1. A preparation method of a nitrogen and sulfur co-doped tungsten disulfide sodium ion battery negative electrode material is characterized by comprising the following steps:
the method comprises the following steps: adding tungsten hexachloride into ethanol, magnetically stirring until the tungsten hexachloride is completely dissolved to form a yellow clear solution, then adding thioacetamide, melamine and trithiocyanuric acid, reacting for 4-48 h at 200-220 ℃ in a hydrothermal kettle, washing, and drying to obtain black powder;
step two: and calcining the black powder under the protection of argon atmosphere to obtain the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery cathode material.
2. The preparation method of the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery anode material as claimed in claim 1, wherein the concentration of the yellow clear solution is 0.025-0.1 mol/L.
3. The preparation method of the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery cathode material as claimed in claim 1, wherein the stirring speed is 600-1000 r/min, and the stirring time is 5-15 min.
4. The preparation method of the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery anode material as claimed in claim 1, wherein the molar ratio of tungsten hexachloride to thioacetamide is 10: 1; the mass ratio of the tungsten hexachloride to the melamine to the trithiocyanuric acid is (7-10): (0.5-2): (0.5-2).
5. The preparation method of the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery anode material as claimed in claim 1, wherein the calcining temperature is 600-1000 ℃ and the calcining time is 1-3 h.
6. The preparation method of the nitrogen and sulfur co-doped tungsten disulfide sodium ion battery anode material as claimed in claim 1, wherein the calcination is performed in a low-temperature tube furnace.
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