CN116613304B - Containing water V 3 O 7 Graphene anode material and preparation method and application thereof - Google Patents

Containing water V 3 O 7 Graphene anode material and preparation method and application thereof Download PDF

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CN116613304B
CN116613304B CN202310897920.7A CN202310897920A CN116613304B CN 116613304 B CN116613304 B CN 116613304B CN 202310897920 A CN202310897920 A CN 202310897920A CN 116613304 B CN116613304 B CN 116613304B
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graphene
metavanadate
aqueous
positive electrode
reaction
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CN116613304A (en
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张宝
程磊
徐宝和
龙祝迪
林可博
邓梦轩
张坤
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Pawa Changsha New Energy Technology Co ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • H01M2004/028—Positive 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

Abstract

The invention belongs to the technical field of zinc ion battery materials, and discloses a water-containing V 3 O 7 -graphene positive electrode material of the general chemical formula nV 3 O 7 ‑(1‑n)V 3 O 7 ·H 2 O-rGO, wherein n is more than or equal to 0.1 and less than or equal to 0.9. The preparation method comprises the following steps: dissolving metavanadate in a reducing organic solvent, and then adding graphene to obtain reaction slurry; adjusting the pH value of the reaction slurry to be 1-4, and performing solvothermal reaction to obtain an intermediate product; calcining the intermediate product in a protective atmosphere to obtain an aqueous V 3 O 7 -graphene positive electrode material. The invention prepares the water-containing V 3 O 7 The method of the graphene anode material is simple and easy to operate, and has no complicated control process and technological process. Containing water V 3 O 7 The graphene positive electrode material can be applied to a zinc ion battery and ensures the cycle performance and capacity retention of the battery.

Description

Containing water V 3 O 7 Graphene anode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of zinc ion battery materials, and particularly relates to a vanadium-based positive electrode material of a zinc ion battery and a preparation method thereof.
Background
In recent years, with the development of energy storage technology, new metal ion batteries including sodium ion batteries, potassium ion batteries, magnesium ion batteries, calcium ion batteries, zinc ion batteries, aluminum ion batteries, and the like have received extensive attention from researchers. Among them, zinc ion batteries are considered as promising candidates for large-scale energy storage due to their low cost and high safety. However, the lack of a suitable positive electrode material having a considerable specific capacity and good durability has hampered practical application of the battery. Vanadium-based cathode materials exhibit higher specific capacities and excellent rate capability, and are also receiving extensive attention from researchers. Patent document US104761114B discloses an aqueous rechargeable zinc-ion battery comprising V 3 O 7 ·H 2 Cathode of O-graphene composite, H is prepared by hydrothermal method 2 V 3 O 8 NW and H 2 V 3 O 8 NW/graphene composite. In a typical synthesis, V will be 2 O 5 The powder (0.364 g) was added to deionized water (20 mL) and the mixture was vigorously stirred. Then, H is 2 O 2 (4 mL) was added to the solution, which was stirred continuously for an additional 2 hours. Subsequently, 20mL of GO solution was added to 14mL of the mixture with vigorous stirring, followed by sonication for 6h. Finally, the solution was transferred to a 50mL autoclave and kept in an oven at 200 ℃ for 5 days. The product was washed several times with ethanol and deionized water and then dried at 60 ℃ to obtain H 2 V 3 O 8 NW/graphene composite. However, V disclosed in the patent document 3 O 7 ·H 2 The preparation method of the O-graphene compound is relatively complicated.
Disclosure of Invention
The main object of the present invention is to provide an aqueous V 3 O 7 -graphene anode material, and preparation method and application thereof.
The following is a specific technical scheme of the invention.
First, the present invention provides a method ofSeed water V 3 O 7 -graphene positive electrode material, the chemical formula of which is represented by nV 3 O 7 -(1-n)V 3 O 7 ·H 2 O-rGO, wherein n is more than or equal to 0.1 and less than or equal to 0.9.
Next, the present invention provides the above-mentioned aqueous V 3 O 7 -a preparation method of graphene positive electrode material, comprising the steps of:
dissolving metavanadate in a reducing organic solvent, and then adding graphene to obtain reaction slurry;
adjusting the pH value of the reaction slurry to be 1-4, and performing solvothermal reaction to obtain an intermediate product;
calcining the intermediate product in a protective atmosphere to obtain an aqueous V 3 O 7 -graphene positive electrode material.
In a further preferred scheme, the metavanadate is at least one of ammonium metavanadate, sodium metavanadate and potassium metavanadate; the reducing organic solvent is at least one of ethanol, methanol, glycol and acetone.
In a further preferred scheme, the concentration of metavanadate in the reaction slurry is 0.5-3 mol/L.
In a further preferred embodiment, the molar ratio of metavanadate to graphene in the reaction slurry is 1:0.05 to 0.15.
In a further preferred scheme, the temperature of the solvothermal reaction is 120-160 ℃, and the time of the solvothermal reaction is 12-20 h.
In a further preferred embodiment, the protective atmosphere is a nitrogen atmosphere.
In a further preferred scheme, the calcination temperature is 250-300 ℃, and the calcination time is 10-60 min.
The present invention also provides an aqueous zinc ion battery comprising the above aqueous V 3 O 7 -graphene positive electrode material.
The invention has the following obvious beneficial technical effects:
the invention prepares the water-containing V 3 O 7 The method of the graphene anode material is simple and easy to operate,without complicated control process and technological flow.
The invention provides the water V 3 O 7 The graphene positive electrode material can be applied to a zinc ion battery and ensures the cycle performance and capacity retention of the battery.
Drawings
Fig. 1 is an HRTEM image of the composite material prepared in example 1.
Fig. 2 is an XPS diagram of C of the positive electrode material prepared in example 1.
Detailed Description
The electrochemical properties of vanadium-based cathode materials with different vanadium-oxygen ratios and different water contents are very different. In exploring vanadium-based materials with ultra-high structural stability and large lattice spacing, the present invention provides vanadium-based positive electrode materials having a chemical formula represented by nV 3 O 7 -(1-n)V 3 O 7 ·H 2 O-rGO, wherein n is more than or equal to 0.1 and less than or equal to 0.9.
In addition, the invention provides a simpler preparation method of the positive electrode material, which comprises the following steps:
dissolving metavanadate in a reducing organic solvent, and then adding graphene to obtain reaction slurry;
adjusting the pH value of the reaction slurry to be 1-4, and performing solvothermal reaction to obtain an intermediate product;
calcining the intermediate product in a protective atmosphere to obtain an aqueous V 3 O 7 -graphene positive electrode material.
V 3 O 7 、(1-n)V 3 O 7 ·H 2 O, rGO are connected by chemical bond with V-O bond and Van der Waals bond with H-O bond and C-O bond. A stable complex phase is formed by chemical bonds and van der waals bonds. The macromolecular structure of water molecules exists in V 3 O 7 In the phase, part of water is lost from the structure in the solvothermal reaction and low-temperature sintering process, so that H-O bonds in the composite material structure are lost, a vacant gap is formed, and the lattice spacing of the composite material is increased. At the same time, the water content in the composite material is kept to be (1-n), and the water content is too high to affect the materialConductivity; the water content is too low, the lattice size in the structure is smaller, and the transmission of zinc hydrate ions is not facilitated.
In the preparation method, metavanadate and graphene undergo solvothermal reaction in a reducing organic solvent, and then an intermediate product is calcined to obtain the water-containing V 3 O 7 The graphene anode material has the advantages of simple preparation method, easy operation and no excessively high requirement on equipment.
In the reaction system, the reducing organic solvent may reduce metavanadate (+5-valent V) to +4.67-valent V. In a specific embodiment of the present invention, the reducing organic solvent is at least one of ethanol, methanol, ethylene glycol and acetone, and the metavanadate is at least one of ammonium metavanadate, sodium metavanadate and potassium metavanadate.
As a further preferable mode, the concentration of metavanadate in the reaction slurry is 0.5-3 mol/L, and the molar ratio of metavanadate to graphene in the reaction slurry is 1:0.05 to 0.15.
And regulating the pH value of the reaction slurry to be 1-4, and carrying out reduction reaction on the organic solvent and metavanadate through solvothermal reaction under an acidic condition.
In the preparation method, the temperature of the solvothermal reaction is 120-160 ℃. The solvothermal reaction temperature is lower than 120 ℃, and the reduction reaction is incomplete; the solvothermal reaction temperature is higher than 160 ℃, and the nano-structures generated by the reaction are aggregated, so that the morphology of the material is finally distributed unevenly. According to the solvothermal reaction process, the reaction time is adaptively adjusted, and in the specific embodiment of the invention, the solvothermal reaction time is 12-20 hours.
In the above preparation process, the step of calcining the intermediate product is also very critical. In the specific embodiment of the invention, the calcination temperature is 250-300 ℃, the calcination temperature is lower than 250 ℃, and the water content in the composite material is too high, so that the conductivity of the material is affected; the calcination temperature is higher than 300 ℃, the water content in the composite material is too low, and the lattice size in the structure is smaller, so that the transmission of zinc hydrate ions is not facilitated. The calcination time is adaptively adjusted according to the conditions of the product in the calcination process. In a specific embodiment of the invention, the calcination time is 10-60 min.
The present invention also provides an aqueous zinc ion battery comprising the above aqueous V 3 O 7 -graphene positive electrode material.
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
0.05mol of ammonium metavanadate is dissolved in 80ml of ethanol solvent, 0.5mmol of rGO is additionally added, the pH value of the reaction system is regulated to 2-2.5 through 3mol/L of hydrochloric acid solution, and then the reaction materials are placed in a polytetrafluoroethylene lining for reaction for 20 hours at 120 ℃ to prepare an intermediate product. And calcining the intermediate product at a low temperature of 250 ℃ for 1h in a nitrogen atmosphere to obtain the composite material.
FIG. 1 is a HRTEM image of a composite material, where the presence of V in the composite material can be determined 3 O 7 、V 3 O 7 H2O, rGO three phases.
The composite material was further subjected to TGA thermogravimetric analysis: 1g of the composite material is used for TGA thermogravimetric test, and after sintering for 5 hours at 350 ℃ under nitrogen atmosphere, the weight loss percentage is 3.35wt%.
Combining the HRTEM image and the TGA thermogravimetric analysis, measuring and calculating that the molecular formula of the composite material is 0.49V 3 O 7 -0.51V 3 O 7 ·H 2 O-rGO。
In addition, FIG. 2 is XPS results for composite C, tests to find the presence of V-O-C chemical bonds.
Comparative example 1
Comparative example 1 differs from example 1 only in that: there is no calcination step.
0.05mol of ammonium vanadate is dissolved in 80ml of ethanol solvent, 0.5mmol of rGO is additionally added, the pH value of the solution is regulated to 2-2.5 by 3mol/L of hydrochloric acid solution, and then the solution is placed in a polytetrafluoroethylene lining for solvothermal reaction at 120 ℃ for 20h, so that the product is prepared.
The molecular formula of the presumed product is V 3 O 7 ·H 2 O@rGO。
Comparative example 2
Comparative example 2 differs from example 1 only in that: the calcination temperature was 500 ℃.
0.05mol of ammonium vanadate is dissolved in 80ml of ethanol solvent, 0.5mmol of rGO is additionally added, the pH value of the solution is regulated to 2-2.5 through 3mol/L hydrochloric acid solution, then the solution is placed in a polytetrafluoroethylene lining for solvothermal reaction at 120 ℃ for 20h, an intermediate product is prepared, and then the intermediate product is calcined at 500 ℃ for 1h under nitrogen atmosphere, so that the final product is obtained.
The final product was further subjected to TGA thermogravimetric analysis: 1g of the composite material is used for TGA thermogravimetric test, and after sintering for 5 hours at 350 ℃ in nitrogen atmosphere, the weight loss percentage of the product is 0wt%.
Example 2
0.1mol of sodium metavanadate was dissolved in 100ml of methanol solvent, 15mmol of rGO was additionally added, the pH value of the solution was adjusted to 1-1.5 by 3mol/L of hydrochloric acid solution, and then the solution was placed in a polytetrafluoroethylene liner and reacted at 160℃for 16 hours to prepare an intermediate product. And then calcining the intermediate product at 300 ℃ for 10min under nitrogen atmosphere to obtain the composite material.
Taking the composite material for TGA thermogravimetric test, sintering for 5 hours at 350 ℃ under nitrogen atmosphere, wherein the weight loss percentage is 5.5wt%, and measuring and calculating that the molecular formula of the composite material is 0.1V 3 O 7 -0.9V 3 O 7 · H 2 O-rGO。
Example 3
Dissolving 0.3mol of potassium metavanadate in 100ml of ethylene glycol and acetone solvent, additionally adding 45mmol of rGO, regulating the pH value of the reaction slurry to 3-4 through a 3mol/L hydrochloric acid solution, and then placing the reaction slurry into a polytetrafluoroethylene lining for solvothermal reaction at 140 ℃ for 16h to prepare an intermediate product. And then calcining the intermediate product at 280 ℃ for 30min under nitrogen atmosphere to obtain the composite material.
Taking 1g of composite material for TGA thermogravimetric test, sintering for 5 hours at 350 ℃ under nitrogen atmosphere, wherein the weight loss percentage is 0.63wt%, and measuring and calculating that the molecular formula of the composite material is 0.9V 3 O 7 -0.1V 3 O 7 · H 2 O-rGO。
The battery assembly was completed by the following method:
the composite materials or products obtained in examples 1-3 and comparative examples 1-2 are taken as positive electrode materials, and are mixed with Acetylene Black (AB) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the mass ratio of 7:2:1, and are mixed in a small beaker at the speed of 800r/min for 2 hours by taking N-methylpyrrolidone (NMP) as a solvent, so as to obtain slurry. And (3) coating the slurry on a current collector stainless steel foil by using an automatic coating machine, horizontally placing the current collector stainless steel foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, and drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven to assemble the CR2032 button cell. The battery takes a pure metal zinc sheet with the diameter of 16mm and the thickness of 0.5mm as a negative electrode, takes a mixed solution of 3M zinc sulfate and 0.05M manganese sulfate as an electrolyte, and takes a glass fiber diaphragm with the model of Whatman GF/D with the diameter of 18mm as a diaphragm.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The specific discharge capacity results of the cells at a voltage of 0.8-1.9V after 100 cycles at a current density of 1A/g are shown in Table 1.
TABLE 1
As apparent from Table 1, the chemical formula of the present invention is represented by nV 3 O 7 -(1-n)V 3 O 7 ·H 2 The O-rGO anode material can enable the zinc ion battery to have better cycle performance and capacity retention rate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. Water-containing V 3 O 7 -graphene positive electrode material characterized in that the positive electrode material has a chemical formula represented by nV 3 O 7 -(1-n)V 3 O 7 ·H 2 O-rGO, wherein n is more than or equal to 0.1 and less than or equal to 0.9; the water V 3 O 7 The preparation method of the graphene anode material comprises the following steps:
dissolving metavanadate in a reducing organic solvent, and then adding graphene to obtain reaction slurry;
adjusting the pH value of the reaction slurry to be 1-4, and performing solvothermal reaction to obtain an intermediate product;
calcining the intermediate product in a protective atmosphere to obtain an aqueous V 3 O 7 -graphene positive electrode material.
2. An aqueous V as claimed in claim 1 3 O 7 -graphene anode material, characterized in that the metavanadate is at least one of ammonium metavanadate, sodium metavanadate and potassium metavanadate; the reducing organic solvent is at least one of ethanol, methanol, glycol and acetone.
3. An aqueous V as claimed in claim 1 or 2 3 O 7 The graphene anode material is characterized in that the concentration of metavanadate in the reaction slurry is 0.5-3 mol/L.
4. An aqueous V as claimed in claim 1 or 2 3 O 7 -graphene cathode material, characterized in that the molar ratio of metavanadate to graphene in the reaction slurry is 1:0.05 to 0.15.
5. The method as claimed in claim 1Is of the formula (I) 3 O 7 The graphene anode material is characterized in that the temperature of the solvothermal reaction is 120-160 ℃, and the time of the solvothermal reaction is 12-20 h.
6. An aqueous V as claimed in claim 1 3 O 7 -graphene cathode material, characterized in that the protective atmosphere is a nitrogen atmosphere.
7. An aqueous V as claimed in claim 1 or 6 3 O 7 The graphene anode material is characterized in that the calcination temperature is 250-300 ℃, and the calcination time is 10-60 min.
8. An aqueous zinc ion battery comprising the aqueous V of any one of claims 1-7 3 O 7 -graphene positive electrode material.
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