CN113130863A - VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery - Google Patents

VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery Download PDF

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CN113130863A
CN113130863A CN202110303802.XA CN202110303802A CN113130863A CN 113130863 A CN113130863 A CN 113130863A CN 202110303802 A CN202110303802 A CN 202110303802A CN 113130863 A CN113130863 A CN 113130863A
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rgo
composite material
graphene oxide
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李星
陈凯建
张磊磊
代书阁
单崇新
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Zhengzhou University
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a VS4/rGO composite material, preparation method thereof, application in zinc ion battery and VS4the/rGO composite comprises the following steps: dispersing graphene oxide in deionized water to form a graphene oxide solution; vanadium source according to molar ratio: 0.6-1.2 of sulfur source: dissolving a vanadium source and a sulfur source in the graphene oxide solution according to the proportion of 0.6-1.5, and stirring to form a uniform premixed solution; dropping into the premixed solution under stirringAdding ammonia water until the pH value of the solution is 9 to obtain a mixed solution; reacting the mixed solution at the temperature of 140 ℃ and 200 ℃ for 24-48 hours; after the reaction is finished and the temperature is cooled to room temperature, cleaning, freezing and drying the obtained product to obtain vanadium tetrasulfide nano-particles/three-dimensional graphene (VS)4/rGO) composite material. VS prepared by the invention4the/rGO composite cathode material is applied to a water-based zinc ion battery, and the capacity, the rate capability and the cycling stability of the water-based zinc ion battery are obviously improved.

Description

VS4/rGO composite material, preparation method thereof and application in zinc ion battery
Technical Field
The invention relates to the technical field of zinc ion battery electrode materials, in particular to VS4a/rGO composite material, a preparation method thereof and application in a zinc ion battery.
Background
The increasing prominence of the problems of fossil fuel exhaustion, environmental pollution and the like makes the development of green new energy technology pay attention. Rechargeable batteries have been widely used in the fields of electronic devices, electric vehicles, and the like due to their advantages of long life, high energy efficiency, simple maintenance, and the like. In view of the safety and high cost of lithium ion batteries, aqueous zinc ion batteries with the advantages of low cost, high safety, environmental friendliness, high power, etc. have been drawing attention. However, although manganese-based and prussian blue cathode materials frequently used in zinc ion batteries at present have high energy density, the rate performance and stability of manganese can be significantly influenced by the dissolution of manganese in an electrolyte; meanwhile, the limited diffusion of zinc ions in the electrolyte also causes the problems of low capacity, attenuation and the like, which greatly limits the large-scale application of the electrolyte. Therefore, the design and preparation technology of the anode material with excellent electrochemical performance still needs to be developed.
In view of the multivalence and polytype of vanadium, vanadium-based compounds can have excellent electrochemical properties, which provides a new direction for the development of positive electrode materials of aqueous zinc-ion batteries. However, the vanadium-based positive electrode materials such as vanadium pentoxide and vanadium dioxide which are researched at present have the problems of low capacity, unstable material structure, poor rate capability and poor cycle stability and the like. As transition metal sulfide, vanadium tetrasulfide (VS)4) Due to the large chain spacing
Figure BDA0002987324260000011
Figure BDA0002987324260000012
And the characteristics of high sulfur content and the like are expected to promote the intercalation/deintercalation process of zinc ions; the weak interactions between chains can also contribute to the charge transport kinetics. Therefore, design and preparation of VS-based4The positive electrode material of (2) is expected to further improve the capacity and cycle stability of the aqueous zinc ion battery.
CN109888223A discloses a preparation method of vanadium tetrasulfide @ reduced graphene oxide composite powder, VS4The graphene oxide is uniformly nucleated on the surface and grows by virtue of the nucleation, and meanwhile, the graphene oxide is reduced to reduced graphene oxide under hydrothermal conditions and becomes very thin, so that VS is formed4Composite structure of bent nanorod in-situ tiled on surface of reduced graphene oxide, in which VS is4The specific surface area of (a) is limited, the contact area of the electrode material and the electrolyte is limited to a certain extent, and the charge transfer and ion transport of the whole battery are influenced.
CN108598432A discloses a preparation method of vanadium tetrasulfide/graphene composite material for sodium ion battery electrode, which is characterized in that vanadium tetrasulfide grows on a layered graphene template or graphene is used for coating vanadium tetrasulfide particles to form a stable solid electrolyte interface film at 0.02 A.g-1The cycle retention rate is 60% after the current is circulated for 50 circles, and the problems of low cycle retention rate, poor long-term stability and the like exist.
Disclosure of Invention
Aiming at the problems of low capacity, poor rate performance, poor cycle stability and the like of a water-based zinc ion battery, the invention develops a simple and low-cost one-step hydrothermal synthesis method, and reductive graphene oxide (rGO) with high mechanical property, high conductivity and three-dimensional structure and vanadium tetrasulfide (VS) with high sulfur content and multiple active sites are synthesized4) Compounding to prepare VS with excellent electrochemical performance4the/rGO composite cathode material is applied to a water system zinc ion battery, and the capacity, the rate capability and the cycling stability of the water system zinc ion battery are obviously improved.
The technical scheme of the invention is realized as follows: VS (virtual switch)4/rGO compositeThe preparation method of the material comprises the following steps:
step 1, dispersing graphene oxide in deionized water to form a graphene oxide solution, wherein the concentration of the graphene oxide solution is 0.5-5 mol/ml;
step 2, vanadium source according to the molar ratio: sulfur source ═ (0.6-1.2): (0.6-1.5), dissolving a vanadium source and a sulfur source in the graphene oxide solution, and stirring to form a uniform premixed solution;
step 3, dropwise adding ammonia water into the premixed solution formed in the step 2 under stirring until the pH value of the solution is 9 to obtain a mixed solution;
step 4, reacting the mixed solution formed in the step 3 at the temperature of 140-200 ℃ for 24-48 hours;
step 5, after the reaction in the step 4 is finished, cooling to room temperature, cleaning, freezing and drying the obtained product to obtain vanadium tetrasulfide nano-particles/three-dimensional graphene (VS)4/rGO) composite material.
Further, in the step 1, the graphene oxide has a sheet diameter of 5-10 μm and 1-5 layers.
Further, in the step 1, ultrasonic dispersion is adopted, the dispersion time is 0.5-1 hour, and the concentration of the graphene oxide aqueous solution is 0.8-2 mol/ml.
Further, in step 2, the vanadium source is sodium orthovanadate or sodium metavanadate, and the sulfur source is thioacetamide or cysteine.
Further, in the step 2, the molar ratio of the vanadium source to the sulfur source is (0.8-1): (0.9-1.2).
Further, in step 2, the stirring speed is 500- "1000 r/min", and the stirring time is 0.5-0.8 h.
Further, in step 4, the reaction temperature is 160-180 ℃, and the reaction time is 24-28 hours.
Further, in step 4, the volume of the mixed solution is 25 to 35 ml.
Further, in step 5, the obtained product is repeatedly washed by deionized water and absolute ethyl alcohol, and then is frozen and dried for 12 to 24 hours at the temperature of between 70 ℃ below zero and 50 ℃ below zero, and optimally, the freezing and drying time is 15 to 20 hours.
VS (virtual switch)4/rGO composites, miningPrepared by the preparation method.
Further, VS4/rGO composites comprising VS4Particles and rGO, VS4The particles are spherical with the particle size of 200-300nm, rGO is a three-dimensional network structure, and VS is adopted4The particles are uniformly attached in a three-dimensional network structure formed by the rGO.
The VS4The application of the/rGO composite material in the anode material of the water system zinc ion battery.
Further, the preparation method of the anode material of the water-based zinc ion battery comprises the following specific steps:
(1) will VS4Mixing the/rGO composite material with acetylene black and a binder according to a mass ratio of 8:1:1, and ultrasonically dispersing the mixture in a small amount of absolute ethyl alcohol to form homogeneous slurry;
(2) uniformly coating the homogeneous slurry in the step (1) on carbon paper, wherein the mass loading capacity is 1-3mg/cm2And drying the coated film at 70 ℃ for 8-15 hours.
Further, the binder is one of polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE).
Further, the mass loading on the carbon paper was 2mg/cm2The drying time is preferably 12 hours.
The invention has the beneficial effects that:
1. VS prepared by adopting one-step hydrothermal method4The particles are spherical with the size of about 200nm, and the rGO shows a three-dimensional network structure; VS4The particles are uniformly attached to a three-dimensional network structure formed by r-GO;
2. VS prepared by the invention40.5Ag of water system zinc ion battery with/rGO composite material as anode material-1Lower 450.3mAh g-1High specific capacity, superior rate capability and long-term stability (at 10 Ag) at high current density-1Capacity retention 94%) after 1000 cycles;
3、VS4the problem of excessive accumulation of reduced graphene oxide is solved; reducing graphene oxide simultaneously also alleviates VS4Agglomeration of the nanoparticles;
4. reduction ofUniformly dispersed VS in graphene oxide framework4The nanoparticles reduce the average path of ion transport in the electrochemical process; the conductivity of the whole electrode is improved by the three-dimensional frame formed by reducing the graphene oxide; the high mechanical strength reduced graphene oxide framework greatly mitigates VS due to ion intercalation during the reaction process4Volume deformation;
5. the invention provides a preparation method which has low cost, simple operation and easy repetition for further improving the electrochemical performance of the water system zinc ion battery from the angle of the structural design of the anode material, and analyzes the microscopic mechanism for improving the electrochemical performance;
6. in the invention, the synthetic VS can be adjusted by adding ammonia water to adjust the pH value of the mixed solution4Effective control of aspect ratio, VS synthesized when pH 94The shape of the particles is spherical, the size of the particles is 200nm, and VS is increased4Provides sufficient sites for ion transport and helps to improve its electrochemical performance, and if pH is not adjusted, synthesized VS4Are nanorods, or exhibit irregular particle shapes and large sizes, which affect the performance of the cell; and the adjustment of pH value also enables the synthesized VS4The nano particles are uniformly dispersed on the three-dimensional net-shaped framework of the rGO, so that the infiltration of electrolyte and the transmission of ions are ensured, and the electrochemical performance of the electrolyte is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is VS in embodiment 1 of the present invention4A preparation flow diagram of/rGO;
FIG. 2 is VS in embodiment 1 of the present invention4XRD pattern of/rGO;
FIG. 3 is VS in embodiment 1 of the present invention4SEM photograph of/rGO;
FIG. 4 is a charge/discharge curve test chart of the assembled aqueous zinc-ion battery according to example 1 of the present invention;
FIG. 5 is a graph of rate performance of an assembled aqueous zinc-ion battery of example 1 of the present invention;
fig. 6 is a test chart of a cycle curve of the assembled aqueous zinc-ion battery of example 1 of the present invention.
Detailed Description
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 obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
As shown in FIG. 1, a VS4The preparation method of the/rGO composite material comprises the following steps:
step 1, ultrasonically dispersing graphene oxide in deionized water to form a graphene oxide solution, wherein the concentration of the graphene oxide solution is 0.5-5 mol/ml;
step 2, vanadium source according to the molar ratio: sulfur source ═ (0.6-1.2): (0.6-1.5), dissolving a vanadium source and a sulfur source in the graphene oxide solution, and stirring to form a uniform premixed solution; a vanadium source: sulfur source ═ (0.6-1.2): (0.6-1.5), synthesized VS4The purity of the nano particles is highest, and the crystallinity is best;
step 3, dropwise adding ammonia water into the premixed solution formed in the step 2 under stirring until the pH value of the solution is 9 to obtain a mixed solution;
step 4, transferring the mixed solution formed in the step 3 into a Teflon high-pressure reaction kettle with a capacity of 50ml of a stainless steel substrate, and then reacting the mixed solution at the temperature of 140-200 ℃ for 24-48 hours;
step 5, after the reaction in the step 4 is finished, cooling to room temperature, cleaning, freezing and drying the obtained product to obtain vanadium tetrasulfide nano-particles/three-dimensional graphene (VS)4/rGO) composite material.
In the step 1, the graphene oxide has the sheet diameter of 5-10 microns and 1-5 layers, and ultrasonic dispersion is adopted, wherein the dispersion time is 0.5-1 hour.
In the step 2, the vanadium source is sodium orthovanadate or sodium metavanadate, the sulfur source is thioacetamide or cysteine, the stirring speed is 500-.
In step 4, the volume of the mixed solution is 25-35 ml. In step 5, the obtained product is repeatedly washed by deionized water and absolute ethyl alcohol, and then is frozen and dried for 12 to 24 hours at the temperature of between 70 ℃ below zero and 50 ℃ below zero, and optimally, the freezing and drying time is 15 to 20 hours.
The VS4The application of the/rGO composite material in the anode material of the water system zinc ion battery.
Further, the preparation method of the anode material of the water-based zinc ion battery comprises the following specific steps:
(1) will VS4Mixing the/rGO composite material with acetylene black and a binder according to a mass ratio of 8:1:1, and ultrasonically dispersing the mixture in a small amount of absolute ethyl alcohol to form homogeneous slurry;
(2) uniformly coating the homogeneous slurry in the step (1) on carbon paper, wherein the mass loading capacity is 1-3mg/cm2And drying the coated film at 70 ℃ for 8-15 hours.
The binder is one of polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE). The mass loading on the carbon paper was 2mg/cm2The drying time is preferably 12 hours.
The chemicals mentioned in the examples of the present invention below are all obtained by legal and conventional commercial means.
Example 1
Carrying out ultrasonic dispersion on graphene oxide for 0.5 hour, and dissolving the graphene oxide in deionized water to form a graphene oxide solution with the concentration of 1 mol/ml; under stirring, the sodium orthovanadate: thioacetamide 0.8: 1, respectively adding the mixture into a graphene oxide aqueous solution, and continuously stirring the mixture for 0.5 hour at a rotating speed of 600r/min to finally form a uniform 30ml premixed solution; then, ammonia water is dropwise added into the premixed solution under stirring until the pH value is 9; then transferring the mixture into a high-pressure reaction kettle at 180 DEG CReacting for 24 hours; after the reaction is finished and the reaction kettle is cooled to room temperature, repeatedly cleaning the generated sample by using deionized water and absolute ethyl alcohol, and then freeze-drying the sample for 24 hours at the temperature of-70 ℃ to obtain VS4a/rGO composite material. VS is divided by mass4/rGO: acetylene black: mixing PTFE at a ratio of 8:1:1, ultrasonically dispersing in a small amount of anhydrous ethanol to form a homogeneous slurry, and adding 2mg/cm of PTFE2The loading was uniformly applied to carbon paper and dried at 70 ℃ for 12 hours. Cutting the carbon paper coated with the slurry into pieces with the area of 1.5cm2The wafer (D) was used as a positive electrode, and had a thickness of 0.3mm and an area of 1.5cm2The zinc sheet (2) was used as a negative electrode, and 1mM zinc trifluoromethanesulfonate was used as an electrolyte to assemble an aqueous zinc ion battery.
FIG. 2 is the synthesized VS4XRD pattern of/rGO corresponding to VS of monoclinic system4(JCPDS: No.72-1294), indicating the synthesized VS4Has high crystallinity and high purity.
The SEM photograph of fig. 3 shows the morphology of the composite material: VS 200-300nm in diameter4The nanoparticles are uniformly distributed in the rGO network in a three-dimensional structure.
FIG. 4 shows the equation VS4The constant current charge-discharge curve of the water system zinc ion battery with the/rGO composite material as the anode under different current densities. As can be seen from the figure, the aqueous zinc ion battery was 0.5A g-1The initial specific discharge capacity can reach 450.3mA h g-1. Even at 10A g-1Can still obtain 313.8mA h g under high current density-1Capacity.
FIG. 5 shows the equation VS4The multiplying power performance curve of the water system zinc ion battery taking the/rGO composite material as the anode. It can be observed that when the current density is from 0.5A g-1The gradient increased to 10A g-1The specific capacity is gradually reduced, and when the specific capacity is recovered to 0.5Ag-1The current density of (2) shows excellent rate performance without deterioration of the capacity of the battery.
FIG. 6 at VS410Ag aqueous zinc ion battery with/rGO composite material as anode-1The cycle stability test below, as shown, still maintains 94% of the initial capacity after 1000 cyclesIt was shown to have excellent cycling stability.
Example 2
Carrying out ultrasonic dispersion on graphene oxide for 0.5 hour, and dissolving the graphene oxide in deionized water to form a graphene oxide solution with the concentration of 1 mol/ml; under stirring, the sodium orthovanadate: thioacetamide 1: 1.2, respectively adding the mixture into the graphene oxide aqueous solution, and continuously stirring the mixture for 0.5 hour at the rotating speed of 600r/min to finally form a uniform 30ml premixed solution; then, ammonia water is dropwise added into the premixed solution under stirring until the pH value is 9; then transferring the mixture into a high-pressure reaction kettle, and reacting for 24 hours at 180 ℃; after the reaction is finished and the reaction kettle is cooled to room temperature, repeatedly cleaning the generated sample by using deionized water and absolute ethyl alcohol, and then freeze-drying the sample for 24 hours at the temperature of-70 ℃ to obtain VS4a/rGO composite material. VS is divided by mass4/rGO: acetylene black: mixing PTFE at a ratio of 8:1:1, ultrasonically dispersing in a small amount of anhydrous ethanol to form a homogeneous slurry, and adding 2mg/cm of PTFE2The loading was uniformly applied to carbon paper and dried at 70 ℃ for 12 hours. Cutting the carbon paper coated with the slurry into pieces with the area of 1.5cm2The wafer (D) was used as a positive electrode, and had a thickness of 0.3mm and an area of 1.5cm2The zinc sheet (2) was used as a negative electrode, and 1mM zinc trifluoromethanesulfonate was used as an electrolyte to assemble an aqueous zinc ion battery.
Example 3
Carrying out ultrasonic dispersion on graphene oxide for 0.5 hour, and dissolving the graphene oxide in deionized water to form a graphene oxide solution with the concentration of 2 mol/ml; under stirring, the sodium orthovanadate: thioacetamide 0.8: 1, respectively adding the mixture into a graphene oxide aqueous solution, and continuously stirring the mixture for 0.5 hour at a rotating speed of 600r/min to finally form a uniform 30ml premixed solution; then, ammonia water is dropwise added into the premixed solution under stirring until the pH value is 9; then transferring the mixture into a high-pressure reaction kettle, and reacting for 24 hours at 180 ℃; after the reaction is finished and the reaction kettle is cooled to room temperature, repeatedly cleaning the generated sample by using deionized water and absolute ethyl alcohol, and then freeze-drying the sample for 24 hours at the temperature of-70 ℃ to obtain VS4a/rGO composite material. VS is divided by mass4/rGO: acetylene black: PTFE-8: 11, ultrasonically dispersing the mixture in a small amount of absolute ethyl alcohol to form a homogeneous slurry, and adding the homogeneous slurry at the concentration of 2mg/cm2The loading was uniformly applied to carbon paper and dried at 70 ℃ for 12 hours. Cutting the carbon paper coated with the slurry into pieces with the area of 1.5cm2The wafer (D) was used as a positive electrode, and had a thickness of 0.3mm and an area of 1.5cm2The zinc sheet (2) was used as a negative electrode, and 1mM zinc trifluoromethanesulfonate was used as an electrolyte to assemble an aqueous zinc ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. VS (virtual switch)4The preparation method of the/rGO composite material is characterized by comprising the following steps:
step 1, dispersing graphene oxide in deionized water to form a graphene oxide solution, wherein the concentration of the graphene oxide solution is 0.5-5 mol/ml;
step 2, vanadium source according to the molar ratio: 0.6-1.2 of sulfur source: dissolving a vanadium source and a sulfur source in the graphene oxide solution according to the proportion of 0.6-1.5, and stirring to form a uniform premixed solution;
step 3, dropwise adding ammonia water into the premixed solution formed in the step 2 under stirring until the pH value of the solution is 9 to obtain a mixed solution;
step 4, reacting the mixed solution formed in the step 3 at the temperature of 140-200 ℃ for 24-48 hours;
step 5, after the reaction in the step 4 is finished, cooling to room temperature, cleaning, freezing and drying the obtained product to obtain VS4a/rGO composite material.
2. A VS as claimed in claim 14The preparation method of the/rGO composite material is characterized in that in the step 1, the sheet diameter of graphene oxide is 5-10 mu m, and the number of layers is 1-5.
3. A VS according to claim 1 or 24of/rGO compositesThe preparation method is characterized in that in the step 1, ultrasonic dispersion is adopted, the dispersion time is 0.5-1 hour, and the concentration of the graphene oxide aqueous solution is 0.8-2 mol/ml.
4. A VS as claimed in claim 14The preparation method of the/rGO composite material is characterized in that in the step 2, a vanadium source is sodium orthovanadate or sodium metavanadate, and a sulfur source is thioacetamide or cysteine.
5. A VS as defined in claim 1 or 44The preparation method of the/rGO composite material is characterized in that in the step 2, the molar ratio of a vanadium source to a sulfur source is 0.8-1: 0.9-1.2.
6. A VS as claimed in claim 14The preparation method of the/rGO composite material is characterized in that in the step 4, the reaction temperature is 160-180 ℃, and the reaction time is 24-28 hours.
7. A VS as claimed in claim 14The preparation method of the/rGO composite material is characterized in that in the step 5, the obtained product is repeatedly washed by deionized water and absolute ethyl alcohol, and then is frozen and dried for 12-24 hours at the temperature of-70 to-50 ℃, and optimally, the freezing and drying time is 15-20 hours.
8. VS prepared by the preparation process according to any of claims 1 to 74the/rGO composite material is characterized in that: including VS4Particles and rGO, VS4The particles are spherical with the particle size of 200-300nm, rGO is a three-dimensional network structure, and VS is adopted4The particles are uniformly attached in a three-dimensional network structure formed by the rGO.
9. VS as set forth in claim 84The application of the/rGO composite material in the anode material of the water system zinc ion battery.
10. The application of the positive electrode material according to claim 9, wherein the preparation method of the positive electrode material of the aqueous zinc-ion battery is as follows:
(1) will VS4Mixing the/rGO composite material with acetylene black and a binder according to a mass ratio of 8:1:1, and ultrasonically dispersing the mixture in a small amount of absolute ethyl alcohol to form homogeneous slurry;
(2) uniformly coating the homogeneous slurry in the step (1) on carbon paper, wherein the mass loading capacity is 1-3mg/cm2And drying the coated film at 70 ℃ for 8-15 hours.
CN202110303802.XA 2021-03-22 2021-03-22 VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery Pending CN113130863A (en)

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CN113611830A (en) * 2021-07-26 2021-11-05 江苏智泰新能源科技有限公司 VS (virtual switch)4-graphene aerogel composite material, preparation method and application
CN114162874A (en) * 2021-12-09 2022-03-11 中国科学技术大学 Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery
CN114188523A (en) * 2021-12-13 2022-03-15 中南大学 Graphene-loaded vanadium pentoxide composite material, preparation method thereof and application thereof in water-based zinc ion battery
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CN115744983A (en) * 2022-11-15 2023-03-07 浙江工业大学 Vanadium-zinc sulfide ion battery positive electrode material and preparation method and application thereof

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CN113611830A (en) * 2021-07-26 2021-11-05 江苏智泰新能源科技有限公司 VS (virtual switch)4-graphene aerogel composite material, preparation method and application
CN114162874A (en) * 2021-12-09 2022-03-11 中国科学技术大学 Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery
CN114162874B (en) * 2021-12-09 2023-03-10 中国科学技术大学 Preparation method of composite metal sulfide loaded mixed carbon material serving as sulfur main body material of lithium-sulfur battery
CN114188523A (en) * 2021-12-13 2022-03-15 中南大学 Graphene-loaded vanadium pentoxide composite material, preparation method thereof and application thereof in water-based zinc ion battery
CN114188523B (en) * 2021-12-13 2024-02-02 中南大学 Graphene-supported vanadium pentoxide composite material, preparation method thereof and application thereof in water-based zinc ion battery
CN114835161A (en) * 2022-04-27 2022-08-02 广东工业大学 Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode, and zinc ion battery
CN114835161B (en) * 2022-04-27 2024-01-19 广东工业大学 Zinc ion battery cathode, preparation method of active material of zinc ion battery cathode and zinc ion battery
CN114843476A (en) * 2022-05-20 2022-08-02 重庆大学 V-shaped groove 3 S 4 Preparation method and application of @ C/G composite electrode material
CN115744983A (en) * 2022-11-15 2023-03-07 浙江工业大学 Vanadium-zinc sulfide ion battery positive electrode material and preparation method and application thereof

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