CN111874950A - Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof - Google Patents
Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111874950A CN111874950A CN202010762965.XA CN202010762965A CN111874950A CN 111874950 A CN111874950 A CN 111874950A CN 202010762965 A CN202010762965 A CN 202010762965A CN 111874950 A CN111874950 A CN 111874950A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- graphene oxide
- electrode material
- tungsten disulfide
- composite electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/626—Metals
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a vanadium-doped tungsten disulfide/graphene oxide composite electrode material and a preparation method and application thereof, and belongs to the technical field of tungsten disulfide nano material preparation. The preparation method of the invention utilizes twoPreparing a vanadium-doped tungsten disulfide/graphene oxide composite electrode material by a hydrothermal method: vanadium is fixed on a graphene oxide substrate by utilizing primary hydrothermal, and then tungsten disulfide nanosheets are grown by utilizing secondary hydrothermal. The preparation method has the advantages of simple operation, low raw material cost, easily controlled reaction temperature and short used time. According to the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the invention, the WS is inhibited by utilizing the larger specific surface area and the better flexibility of the graphene oxide2The agglomeration of the nano-sheets and the doping of vanadium provides active sites, so that the electrochemical performance of the material is improved, and the material has wide research value and application value in the electrochemical field.
Description
Technical Field
The invention belongs to the technical field of preparation of tungsten disulfide nano materials, and relates to a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, and a preparation method and application thereof.
Background
Layered tungsten disulfide (WS)2) The transition metal sulfide (TMD) is one of transition metal sulfides (TMD) which is discovered at the earliest and is researched more, has weak interlayer Van der Waals force shared by a TMD family, is easy to prepare into a single-layer or multi-layer nano sheet by peeling, and has wide application prospect in energy storage devices due to better stability and semiconductor characteristics of a nano structure. The layered structure of the TMD nano material is Li+The migration of ions in the charging and discharging process is facilitated, and MoS2And WS2As a representative of TMD materials, Li can be used as an electrode material of a lithium ion battery+Ions are relatively easily intercalated or deintercalated from the electrode material.
Although WS2Has larger specific surface area, but has lower electron mobility and can provide smaller capacitance, so the photoelectric property and the electrochemical property of the material are improved by compounding or element doping with other materials. The graphene oxide has large specific surface area and good flexibility, and can be used as a material for preparing a material for a printed circuit boardGrowth of WS2An ideal substrate for the nanoplatelets. The composite graphene oxide can effectively inhibit WS2The agglomeration among the nano sheets effectively improves the circulation stability of the nano sheets. However, tungsten disulfide itself belongs to a semiconductor material, and the conductivity of tungsten disulfide is poor, so that the problem of electrochemical reaction lag exists in the charge-discharge reaction process, and the rate capability of tungsten disulfide is poor. Therefore, the conductivity of the material can be improved and the active positioning points can be increased by doping the metal elements so as to improve the rate capability. Most of the doping methods at present mainly use chemical vapor deposition, which generally has higher synthesis temperature and higher energy consumption. And chemical vapor deposition is suitable for bulk materials, and the uniformity of the product is difficult to control. On the other hand, the potassium storage capacity of WS2 electrode has been studied.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, and a preparation method and application thereof. The preparation method disclosed by the invention utilizes two hydrothermal reactions to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material. The experimental operation process is simple and easy to control, and the raw material cost is low; by the preparation method, the vanadium-doped tungsten disulfide/graphene oxide composite electrode material can be prepared in a large scale in a short time, and the vanadium-doped tungsten disulfide/graphene oxide composite electrode material is applied to a potassium ion battery cathode material to show excellent potassium storage performance, so that the vanadium-doped tungsten disulfide/graphene oxide composite electrode material has wide research value and application value in the electrochemical field.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, which comprises the following steps:
1) uniformly dispersing graphene oxide and sodium metavanadate in water to obtain a solution A; carrying out hydrothermal homogeneous reaction on the solution A, and cooling to obtain a product system A containing a vanadium simple substance graphene oxide matrix;
2) uniformly dispersing tungsten hexachloride and thioacetamide in a product system A to obtain a suspension B; carrying out hydrothermal reaction on the suspension B to grow tungsten disulfide nanosheets, and cooling to obtain a product system B; centrifugally washing the product system B, and then freeze-drying to collect powder to obtain the vanadium-doped tungsten disulfide/graphene oxide composite material;
3) and calcining and annealing the vanadium-doped tungsten disulfide/graphene oxide composite material to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material.
Preferably, in the step 1), the reaction charge ratio of the graphene oxide, the sodium metavanadate, the water, the tungsten hexachloride and the thioacetamide is (30-60) mg, (0.0073-0.073) g, (30-60) mL, (0.238-2.38) g and (0.45-4.5) g.
Preferably, in the step 1), the reaction temperature of the hydrothermal reaction is 180-220 ℃, and the reaction time is 12-36 h.
Preferably, in the step 2), the reaction temperature is 200-240 ℃ and the reaction time is 12-48 h.
Preferably, in the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 6 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
Preferably, the calcination annealing treatment in step 3) specifically includes: the calcination temperature is 500-800 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
The invention also discloses the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method.
Preferably, the capacity of the composite electrode material reaches 368mAh & g-1(ii) a At 1 A.g-1After the current density of (2) is cycled for 500 cycles, the capacity retention rate is 88.7%.
The invention also discloses application of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material as a battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material, which comprises the steps of firstly fixing simple substance vanadium on a Graphene Oxide (GO) substrate by utilizing primary hydrothermal, and then growing tungsten disulfide (WS) on the GO substrate fixed with the simple substance vanadium by utilizing secondary hydrothermal2) Nanosheet, to obtainTo vanadium doped tungsten disulfide/graphene oxide (WS)2/GO) composite electrode material. The invention prepares the vanadium-doped WS by a two-step hydrothermal method2the/GO composite electrode material is prepared into the nano-sized vanadium-doped tungsten disulfide/graphene oxide composite electrode material with uniform appearance without high-temperature treatment, and the preparation method has the advantages of simple and efficient preparation process, low raw material cost and easily-controlled reaction temperature.
The invention also discloses the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method. The composite electrode material utilizes the graphene oxide with larger specific surface area and better flexibility, and can effectively inhibit WS2The agglomeration among the nano sheets and the introduction of vanadium doping provide more active sites, so that the electrochemical performance of the material is greatly improved.
Furthermore, the cycle performance test proves that the capacity of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the invention can reach 368 mAh.g when the vanadium-doped tungsten disulfide/graphene oxide composite electrode material is activated by small current-1Higher capacity is exhibited; at 1 A.g-1After circulating for 500 cycles at a current density of 158mAh g-1The capacity retention rate was 88.7%, showing excellent capacity retention rate performance.
The invention also discloses application of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material to a battery cathode material. Through relevant experimental detection, the vanadium-doped tungsten disulfide/graphene oxide composite electrode material shows excellent potassium storage performance, so that the vanadium-doped tungsten disulfide/graphene oxide composite electrode material has wide research value and application value in the electrochemical field.
Drawings
Fig. 1 is an X-ray diffraction pattern of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in example 3 of the present invention;
fig. 2 is a scanning electron microscope image of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in embodiment 3 of the present invention; wherein, (a) is a low-power graph and (b) is a high-power graph;
fig. 3 is a transmission electron microscope image of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in embodiment 3 of the present invention;
fig. 4 is an energy spectrum of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared in example 3 of the present invention; wherein, (a) is the shape of the selected area, (b) is C, W, S, V element distribution, (C) is C element, (d) is W element, (e) is S element, and (f) is V element;
fig. 5 is a cycle performance diagram of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material for a negative electrode material of a potassium ion battery, which is prepared in embodiment 3 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses vanadium-doped tungsten disulfide/graphene oxide (WS)2The preparation method of the/GO) composite electrode material comprises the following steps:
the method comprises the following steps: and adding 30-60 mg of GO into 30-60 mL of deionized water, and carrying out ultrasonic treatment for 6-12h to obtain a uniform brown solution A. Adding 0.0073-0.073 g of sodium metavanadate, and controlling the GO concentration to be 0.5-2 mg/ml.
Step two: and transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the temperature of 180-220 ℃ for 12-36 h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 0.238-2.38 g of tungsten hexachloride and 0.45-4.5 g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500-800 r/min, and the stirring time is 30-120 min.
Step four: and transferring the solution B into a homogeneous reactor to carry out secondary hydrothermal reaction at 200-240 ℃ for 12-48 h, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, and drying the product in a freeze dryer at the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for 6-12 hours.
Step six: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 500-800 ℃, the heat preservation time is 1-4 h, and the heating rate is 5-20 ℃/min. Obtaining vanadium doped WS2a/GO composite electrode material.
The present invention is described in further detail below with reference to specific examples:
example 1
The method comprises the following steps: 60mg of GO is added into 30mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.058g of sodium metavanadate is added, and the concentration of GO is controlled to be 2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 180 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.65g of tungsten hexachloride and 2.28g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500r/min, and the stirring time is 30 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 200 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4 times, and drying the product in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 10Pa for 6 hours. Obtaining vanadium doped WS2a/GO composite electrode material.
Example 2
The method comprises the following steps: 30mg of GO is added into 60mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.073g of sodium metavanadate was added, controlling the GO concentration to 0.5 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 36h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 0.238g of tungsten hexachloride and 0.45g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 800r/min, and the stirring time is 120 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 240 ℃, the reaction time is 48 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 40Pa for 12 hours. Obtaining vanadium doped WS2a/GO composite electrode material.
Example 3
The method comprises the following steps: 60mg of GO is added into 60mL of deionized water, and the mixture is subjected to ultrasonic treatment for 12 hours to obtain a uniform brown solution A. 0.045g of sodium metavanadate is added, and the concentration of GO is controlled to be 1 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 200 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.19g of tungsten hexachloride and 2.25g of thioacetamide into the kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 700r/min, and the stirring time is 60 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 200 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer with the temperature of-40 ℃ and the vacuum degree of 40Pa for 12 hours. Obtaining vanadium doped WS2a/GO composite electrode material.
Example 4
The method comprises the following steps: 45mg of GO is added into 45mL of deionized water, and the mixture is subjected to ultrasonic treatment for 10 hours to obtain a uniform brown solution A. 0.073g of sodium metavanadate was added, controlling the GO concentration to 1 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for carrying out homogeneous reaction at the reaction temperature of 200 ℃ for 36h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 2.38g of tungsten hexachloride and 4.45g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 500r/min, and the stirring time is 75 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 220 ℃, the reaction time is 36 hours, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer with the temperature of-60 ℃ and the vacuum degree of 30Pa for 8 hours. Obtaining vanadium doped WS2a/GO composite electrode material.
Example 5
The method comprises the following steps: 60mg of GO is added into 50mL of deionized water, and the mixture is subjected to ultrasonic treatment for 8 hours to obtain a uniform brown solution A. 0.0098g of sodium metavanadate is added, and the concentration of GO is controlled to be 1.2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 180 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 2.07g of tungsten hexachloride and 3.68g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 600r/min, and the stirring time is 45 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 210 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step five: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer at the temperature of-50 ℃ and the vacuum degree of 35Pa for 8 hours. Obtaining vanadium doped WS2a/GO composite electrode material.
Example 6
The method comprises the following steps: 60mg of GO is added into 50mL of deionized water, and the mixture is subjected to ultrasonic treatment for 8 hours to obtain a uniform brown solution A. 0.0073g of sodium metavanadate is added, and the concentration of GO is controlled to be 1.2 mg/ml.
Step two: and (3) transferring the solution A to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step three: and opening the reaction kettle, adding 1.65g of tungsten hexachloride and 4.5g of thioacetamide into the reaction kettle, and magnetically stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension B, wherein the stirring speed is 600r/min, and the stirring time is 45 min.
Step four: and transferring the solution B into a homogeneous reaction instrument for secondary hydrothermal reaction, wherein the reaction temperature is 240 ℃, the reaction time is 18h, and naturally cooling to room temperature after the reaction is finished.
Step five: opening the reaction kettle, taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, centrifugally separating, and repeatingWashing for 5 times, and drying in a freeze dryer at-50 deg.C and vacuum degree of 40Pa for 6 hr. Obtaining vanadium doped WS2a/GO composite electrode material.
In conclusion, the invention utilizes a two-step hydrothermal method to obtain vanadium-doped WS2the/GO composite electrode material has the advantages of simple experimental operation process, low raw material cost, easy control of reaction temperature and short used time. GO is used as a substrate to grow tungsten disulfide nanosheets, and GO has a large specific surface area and good flexibility and can effectively inhibit WS2The agglomeration among the nano sheets effectively improves the circulation stability of the nano sheets. Doping vanadium into WS2the/GO composite material improves the conductivity of the material, increases the active positioning points and greatly improves the rate capability of the material.
The invention is described in further detail below with reference to the accompanying drawings:
see FIG. 1 for vanadium doped WS prepared in example 32An X-ray diffraction (XRD) pattern of the/GO composite electrode material; sample and WS of hexagonal system having JCPDS number 08-02372The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists.
FIG. 2 shows the vanadium doped WS prepared in example 32Scanning Electron Microscope (SEM) pictures of the/GO composite electrode material. The tungsten disulfide nanosheets uniformly grow on the surface of the graphene oxide.
FIG. 3 shows the vanadium doped WS prepared in example 32And (4) a Transmission Electron Microscope (TEM) picture of the/GO composite electrode material. The result is consistent with the scan result.
FIG. 4 shows the preparation of vanadium doped WS2The energy spectrum of the/GO composite electrode material can see that W, S, C, V and other elements are uniformly distributed, and the vanadium exists in a doped form by combining the fact that no obvious peak of vanadium or vanadium compounds exists in XRD.
FIG. 5 shows vanadium doped WS2the/GO composite material is used as a potassium ion battery cathode material and has the cycle performance under high current. It can be seen that the capacity of the catalyst can reach 368 mAh.g when the catalyst is activated by small current-1Higher capacity is exhibited. After 1 A.g-1After circulating for 500 cycles at a current density of 158mAh g-1The capacity retention rate is 88.7%, and the excellent potassium storage performance is shown.
Analysis of the samples with a Japan science D/max2000 PCX-ray diffractometer (vanadium doped WS)2/GO composite) found with WS of hexagonal system with JCPDS numbers 08-02372The structures are consistent, which shows that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists. The sample is observed by a Field Emission Scanning Electron Microscope (FESEM) and a transmission electron microscope, and the tungsten disulfide nanosheet can be uniformly grown on the graphene oxide. And the prepared product has better dispersibility and uniform size distribution. The observed appearance and scanning of the transmission are consistent, and the uniform distribution of W, S, C, V elements and the like can be seen from the energy spectrum test, which indicates that the vanadium-doped WS is successfully synthesized2the/GO composite material is found to have excellent potassium storage performance from electrochemical performance tests.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a vanadium-doped tungsten disulfide/graphene oxide composite electrode material is characterized by comprising the following steps:
1) uniformly dispersing graphene oxide and sodium metavanadate in water to obtain a solution A; carrying out hydrothermal homogeneous reaction on the solution A, and cooling to obtain a product system A containing a vanadium simple substance graphene oxide matrix;
2) uniformly dispersing tungsten hexachloride and thioacetamide in a product system A to obtain a suspension B; carrying out hydrothermal reaction on the suspension B to grow tungsten disulfide nanosheets, and cooling to obtain a product system B; centrifugally washing the product system B, and then freeze-drying to collect powder to obtain the vanadium-doped tungsten disulfide/graphene oxide composite material;
3) and calcining and annealing the vanadium-doped tungsten disulfide/graphene oxide composite material to obtain the vanadium-doped tungsten disulfide/graphene oxide composite electrode material.
2. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the reaction charge ratio of graphene oxide, sodium metavanadate, water, tungsten hexachloride and thioacetamide is (30-60) mg, (0.0073-0.073) g, (30-60) mL, (0.238-2.38) g and (0.45-4.5) g.
3. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 1), the reaction temperature of the hydrothermal reaction is 180-220 ℃, and the reaction time is 12-36 h.
4. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 2), the reaction temperature is 200-240 ℃ and the reaction time is 12-48 h.
5. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein in the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 6 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
6. The preparation method of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 1, wherein the calcination annealing treatment in the step 3) specifically comprises: the calcination temperature is 500-800 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-4 h.
7. The vanadium-doped tungsten disulfide/graphene oxide composite electrode material prepared by the preparation method of any one of claims 1 to 6.
8. The vanadium-doped tungsten disulfide/graphene oxide composite electrode material of claim 7, wherein the composite electrode material is prepared byThe capacity of the electrode material reaches 368mAh g-1(ii) a At 1 A.g-1After the current density of (2) is cycled for 500 cycles, the capacity retention rate is 88.7%.
9. Use of the vanadium-doped tungsten disulfide/graphene oxide composite electrode material according to claim 7 or 8 as a battery negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010762965.XA CN111874950B (en) | 2020-07-31 | 2020-07-31 | Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010762965.XA CN111874950B (en) | 2020-07-31 | 2020-07-31 | Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111874950A true CN111874950A (en) | 2020-11-03 |
| CN111874950B CN111874950B (en) | 2022-07-29 |
Family
ID=73204481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010762965.XA Active CN111874950B (en) | 2020-07-31 | 2020-07-31 | Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111874950B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115112737A (en) * | 2022-06-27 | 2022-09-27 | 天津大学 | Preparation and application of nitrogen-doped reduced graphene oxide-based composite tungsten disulfide nanosheet electrochemical sensor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142550A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Compound nano material of graphene nano slice and WS2 and preparation method thereof |
| CN105668636A (en) * | 2016-04-06 | 2016-06-15 | 江苏理工学院 | Vanadium-doped tungsten disulfide nanosheet material and preparation method thereof |
| CN108735519A (en) * | 2018-06-04 | 2018-11-02 | 广东工业大学 | A kind of preparation method and applications of graphene/vanadic anhydride composite material |
| CN109326787A (en) * | 2018-10-30 | 2019-02-12 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/GO combination electrode material |
| CN109888223A (en) * | 2019-02-26 | 2019-06-14 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@redox graphene composite granule |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
-
2020
- 2020-07-31 CN CN202010762965.XA patent/CN111874950B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142550A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Compound nano material of graphene nano slice and WS2 and preparation method thereof |
| CN105668636A (en) * | 2016-04-06 | 2016-06-15 | 江苏理工学院 | Vanadium-doped tungsten disulfide nanosheet material and preparation method thereof |
| CN108735519A (en) * | 2018-06-04 | 2018-11-02 | 广东工业大学 | A kind of preparation method and applications of graphene/vanadic anhydride composite material |
| CN110600682A (en) * | 2018-06-12 | 2019-12-20 | 天津大学 | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof |
| CN109326787A (en) * | 2018-10-30 | 2019-02-12 | 陕西科技大学 | A kind of preparation method of tungsten disulfide/GO combination electrode material |
| CN109888223A (en) * | 2019-02-26 | 2019-06-14 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@redox graphene composite granule |
Non-Patent Citations (1)
| Title |
|---|
| XIAODONG XU 等: "Freeze-dried WS2composites with low content of graphene as high-rate lithium storage materials", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115112737A (en) * | 2022-06-27 | 2022-09-27 | 天津大学 | Preparation and application of nitrogen-doped reduced graphene oxide-based composite tungsten disulfide nanosheet electrochemical sensor |
| CN115112737B (en) * | 2022-06-27 | 2024-05-07 | 天津大学 | Preparation and application of electrochemical sensor based on nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111874950B (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Surfactant-dependent flower-and grass-like Zn 0.76 Co 0.24 S/Co 3 S 4 for high-performance all-solid-state asymmetric supercapacitors | |
| CN105633483B (en) | A kind of preparation method of sodium-ion battery cathode SnSe/Graphene combination electrode materials | |
| CN106299365A (en) | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery | |
| CN108695495B (en) | Reduced graphene oxide modified antimony trisulfide battery cathode material | |
| CN108269982B (en) | Composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN102804463A (en) | Cathode active material for a lithium rechargeable battery and a production method therefor | |
| CN107337205B (en) | Method for converting waste corn straw into sodium-ion battery electrode material | |
| CN108011085B (en) | Lithium-sulfur battery positive electrode material, and preparation method and application thereof | |
| CN106935823A (en) | A kind of lithium ion battery negative material Sn/C and preparation method thereof | |
| CN106058206A (en) | Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof | |
| CN105280897A (en) | Preparation method for C/ZnO/Cu composite material of anode material of lithium ion battery | |
| CN108963215B (en) | N-doped graphene flexible substrate fixed porous MoS with three-dimensional structure2Nano material and preparation method and application thereof | |
| CN111554912A (en) | Tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and preparation method thereof | |
| CN114242983A (en) | V-shaped groove3S4@ C composite material and preparation method and application thereof | |
| CN107026263B (en) | Sea urchin-shaped bismuth sulfide/macroporous graphene composite material, preparation method and application thereof | |
| CN111874950B (en) | Vanadium-doped tungsten disulfide/graphene oxide composite electrode material and preparation method and application thereof | |
| CN115207344B (en) | Preparation of FexSey@CN composite material and electrochemical energy storage application thereof | |
| CN113782713B (en) | MoS 2 Nano-sheet vertically embedded biological carbon nano composite material and preparation method and application thereof | |
| CN109473634B (en) | Method for solid-phase co-thermal synthesis of molybdenum diselenide/nitrogen-doped carbon rod | |
| CN107342404B (en) | Carbon modified MoS2/MoO2Two-phase composite material and preparation method thereof | |
| CN113410459A (en) | Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application | |
| Li et al. | Controllable solvo-hydrothermal electrodeposition of lithium vanadate uniform carnation-like nanostructure and their electrochemical performance | |
| CN104934577A (en) | Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material | |
| CN111573745A (en) | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur | |
| CN101420031B (en) | Electrochemical magnesium ionic insertion/deinsertion electrode and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |