CN114914423B - Composite material of zinc vanadate coated carbon microsphere, and preparation method and application thereof - Google Patents

Composite material of zinc vanadate coated carbon microsphere, and preparation method and application thereof Download PDF

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CN114914423B
CN114914423B CN202210580247.XA CN202210580247A CN114914423B CN 114914423 B CN114914423 B CN 114914423B CN 202210580247 A CN202210580247 A CN 202210580247A CN 114914423 B CN114914423 B CN 114914423B
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zinc
carbon microsphere
composite material
zinc vanadate
vanadate
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CN114914423A (en
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杨佳婍
蒋铭熙
潘丽坤
徐敏
陆婷
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East China Normal 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention provides a composite material of zinc vanadate coated carbon microspheres, which structurally comprises carbon microspheres and zinc vanadate nanosheets, wherein the carbon microspheres are coated by the zinc vanadate nanosheets; a method for preparing a composite material of zinc vanadate coated carbon microspheres, comprising the following steps: 1. preparing carbon microspheres by a hydrothermal method; 2. coating the carbon microspheres by zinc vanadate nanosheets by a hydrothermal method and a heat treatment method; the composite material of the zinc vanadate coated carbon microsphere is used as a positive electrode material of a water-based zinc ion battery. The composite material of the zinc vanadate coated carbon microsphere prepared by the invention can effectively improve the electrochemical performance of a water system zinc ion battery.

Description

Composite material of zinc vanadate coated carbon microsphere, and preparation method and application thereof
Technical Field
The invention relates to a zinc vanadate coated carbon microsphere composite material, and a preparation method and application thereof, and belongs to the technical field of new energy materials.
Background
With the continuous development of society and the progress of technology, electronic products are becoming more and more common, and energy storage becomes vital; traditional lithium ion batteries cannot be produced and applied in large scale to meet the demands of the energy storage market due to inherent unsafe and expensive processing costs; in recent years, the aqueous zinc ion battery is a popular candidate for the lithium ion battery due to the characteristics of environmental protection, high safety, large-scale development and the like.
Vanadium oxides and their complexes, manganese oxides and their complexes, prussian blue analogues and bimetallic compounds have so far been the most commonly used aqueous zinc ion battery cathode materials; the vanadium oxide has an inherent lamellar or tunnel-shaped special structure, so that ion diffusion is efficient and feasible, and the vanadium oxide becomes a common material in a water-based zinc ion battery; however, the poor rate capability and poor cycle stability of pure vanadium oxide are not neglected, because pure vanadium oxide has poor conductivity, is unfavorable for electron transmission, and hinders electrochemical reaction, thereby affecting the rate capacity thereof; in addition, volume expansion easily occurs during circulation, and the internal structure rapidly collapses, resulting in rapid capacity decay and poor circulation stability.
Vanadium-based bimetallic oxides (e.g. Fe 2 VO 4 、CaV 2 O 7 Etc.) have come into wide view in recent years due to their unique structure and superior physicochemical properties, have been widely focused and applied in various fields of energy storage, catalysis, etc., in which zinc vanadate has been used for its zinc-rich property and multi-electron transport property due to vanadium, and Zn during primary charging 2+ Can be separated out to bring extra metal vacancies to improve the capacity, so that the zinc-ion battery anode material is very suitable for being used as an anode material of a water-based zinc-ion battery; however, the zinc vanadate material can be used as the positive electrode material of the water-based zinc ion battery, and the capacity is generally low, and the safety of the preparation process is low, so that the research on the zinc vanadate preparation method with controllable morphology, simple and convenient operation and high safety is very significant on the premise of ensuring the discharge capacity.
Disclosure of Invention
The invention provides a zinc vanadate coated carbon microsphere composite material, and a preparation method and application thereof, and aims to prepare a positive electrode material applicable to a water-based zinc ion battery.
The technical solution of the invention is as follows: the composite material of the zinc vanadate coated carbon microsphere structurally comprises the carbon microsphere and a zinc vanadate (Zn 3V3O 8) nanosheet, wherein the zinc vanadate (Zn 3V3O 8) nanosheet coats the carbon microsphere.
Further, the particle diameter of the carbon microsphere is preferably in the range of 1 μm to 10. Mu.m.
Further, the thickness of the zinc vanadate (Zn 3V3O 8) nanosheets is preferably 10nm to 200nm.
A method for preparing a composite material of zinc vanadate coated carbon microspheres, comprising the following steps:
1. preparing carbon microspheres by a hydrothermal method;
2. and coating the carbon microspheres by the zinc vanadate nanosheets by a hydrothermal method and a heat treatment method.
Further, the preparation of the carbon microsphere by the hydrothermal method specifically comprises the following steps:
1-1, preparing a glucose solution;
1-2, adding a pH value regulator and a formaldehyde aqueous solution into the glucose solution, and fully stirring to form a mixed solution;
1-3, carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product;
1-4, centrifuging the hydrothermal reaction product, and collecting to obtain a first precipitate;
1-5, performing vacuum freeze drying on the collected first precipitate to obtain the carbon microsphere.
Further, the method for coating the carbon microsphere by the zinc vanadate nanosheets by using a hydrothermal method and a heat treatment method comprises the following steps:
2-1, pouring ethylene glycol into a container;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
2-3, adding the carbon microspheres prepared in the step 1 into the suspension, and continuing until the carbon microspheres are uniformly dispersed;
2-4, carrying out solvothermal reaction on the suspension dispersed with the carbon microspheres to obtain a solvothermal reaction product;
2-5, centrifuging the solvothermal reaction product, and collecting a second precipitate;
2-6, vacuum freeze-drying the collected second precipitate;
2-7, carrying out heat preservation on the dried product for a certain time at the heat preservation temperature in the nitrogen atmosphere to obtain the zinc vanadate nanosheet coated carbon microsphere composite material.
Further, the pH regulator is preferably sodium hydroxide and citric acid, and the pH regulator is used for regulating the pH value to be 8; the solubility of the glucose solution is preferably 0.23mol/L to 0.38mol/L; the concentration of the formaldehyde aqueous solution is preferably 0.37mol/L to 0.40 mol/L; the solubility of the glucose solution is further preferably 0.38mol/L; the concentration of the aqueous formaldehyde solution is further preferably 0.40 mol/L.
Further, the mixed solution is subjected to hydrothermal reaction to obtain a hydrothermal reaction product, which is specifically as follows: pouring the mixed solution into a polytetrafluoroethylene mould, and performing a hydrothermal reaction to obtain a hydrothermal reaction product; the hydrothermal reaction condition is preferably 160 ℃ for 4-6 hours; the hydrothermal reaction condition is further preferably 160 ℃ for 6 hours.
Further, the specific method for centrifuging the hydrothermal reaction product comprises the following steps: alternate centrifugation was performed with deionized water and ethanol at 8000 r/min.
Further, the first precipitate collected is freeze-dried in vacuum, specifically: the collected first precipitate was freeze-dried in vacuo for 48h at-80 ℃.
Further, the concentration of the ammonium metavanadate in ethylene glycol is preferably 0.10mol/L to 0.15mol/L; the concentration of the zinc triflate in the ethylene glycol is preferably 0.030 mol/L-0.035 mol/L; the concentration of polyvinylpyrrolidone in ethylene glycol is preferably 1.55 g/L-1.70 g/L; the concentration of the carbon microsphere in ethylene glycol is preferably 10 g/L.
Further, the suspension dispersed with the carbon microspheres is subjected to solvothermal reaction to obtain a solvothermal reaction product, which is specifically as follows: pouring the suspension with the carbon microspheres into a polytetrafluoroethylene mould for solvothermal reaction; the reaction condition of the solvothermal reaction is 180 ℃ for 8-12 h; the reaction condition of the solvothermal reaction is further preferably 180 ℃ for 12 hours.
Further, the specific method for centrifuging the solvothermal reaction product comprises the following steps: alternate centrifugation was performed with deionized water and ethanol at 8000 r/min.
Further, the second precipitate collected is freeze-dried in vacuum, specifically: the collected second precipitate was lyophilized in vacuo for 48h at-80 ℃.
Further, the heat preservation temperature is preferably 400-600 ℃; the heat preservation temperature is specifically that the temperature is raised from the room temperature to the heat preservation temperature at a heating rate of 5 ℃/min; the heat preservation is carried out for a certain time for 6 hours; the holding temperature is further preferably 600 ℃.
The composite material of the zinc vanadate coated carbon microsphere is used as a positive electrode material of a water-based zinc ion battery.
The application of the composite material of the zinc vanadate coated carbon microsphere specifically comprises the following steps: and dispersing the composite material of the zinc vanadate nanosheets coated with the carbon microspheres, the conductive carbon black and the polyvinylidene fluoride in the mass ratio of 7:2:1 in N-methylpyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven under a vacuum condition to obtain the water-based zinc ion battery anode material.
The invention has the beneficial effects that:
the zinc vanadate coated carbon microsphere composite material prepared by the preparation method provided by the invention is used for the positive electrode of a water system zinc ion battery, and the zinc vanadate with an ultrathin nanosheet structure can improve the ion transmission rate, shorten the time of ion diffusion and transfer and is beneficial to the performance improvement of an electrochemical diffusion control process; in addition, the unique spherical structure of the integral composite material formed by the zinc vanadate nanosheets coated with the carbon microspheres has a relatively high specific surface area, so that the contact area between the active material and the electrolyte can be increased, the ion diffusion path can be shortened, and more space can be provided for volume expansion in the charge and discharge processes; in summary, the zinc vanadate coated carbon microsphere composite material prepared by the invention can effectively improve the electrochemical performance of the water-based zinc ion battery.
Drawings
FIG. 1 is a scanning electron microscope photograph of a composite material of ultrathin zinc vanadate nanosheets coated with carbon microspheres prepared in example 1 of the invention.
Fig. 2 is a scanning electron microscope photograph of a composite material of ultrathin zinc vanadate nanosheets coated with carbon microspheres prepared in example 2 of the invention.
Fig. 3 is a scanning electron microscope photograph one of the composite material of the ultrathin zinc vanadate nanosheets coated with carbon microspheres prepared in example 3 of the invention.
Fig. 4 is a second sem photograph of the composite material of the ultrathin zinc vanadate nanosheet-coated carbon microsphere prepared in example 3 of the invention.
Figure 5 is an XRD pattern for the product prepared in example 1 of the present invention.
Figure 6 is an XRD pattern for the product prepared in example 2 of the present invention.
Figure 7 is an XRD pattern for the product prepared in example 3 of the present invention.
Fig. 8 is a graph of five charge and discharge tests of the composite material of the ultrathin zinc vanadate nanosheets coated with carbon microspheres as the positive electrode in the same current density in the aqueous zinc ion battery according to embodiment 1 of the invention.
Fig. 9 is a graph of five charge and discharge tests of the composite material of the ultrathin zinc vanadate nanosheets coated with carbon microspheres as the positive electrode in the same current density in the aqueous zinc ion battery according to embodiment 2 of the invention.
Fig. 10 is a graph of five charge and discharge tests of the composite material of the ultrathin zinc vanadate nanosheets coated with carbon microspheres as the positive electrode in the same current density in the aqueous zinc ion battery according to embodiment 3 of the invention.
FIG. 11 is a graph showing the rate performance of the composite material of the ultrathin zinc vanadate nanosheets coated with carbon microspheres as a positive electrode in a water-based zinc ion battery according to examples 1 to 3 of the invention.
Detailed Description
The composite material of the zinc vanadate coated carbon microsphere structurally comprises the carbon microsphere and a zinc vanadate (Zn 3V3O 8) nanosheet, wherein the zinc vanadate (Zn 3V3O 8) nanosheet coats the carbon microsphere.
The particle diameter of the carbon microspheres is preferably in the range of 1 μm to 10 μm, more preferably 4 μm to 8 μm; the ultra-thin vanadate type nano-sheet is loaded by taking the carbon microspheres with uniform size as a template, so that controllable conditions are provided for the morphology of the composite material, and similarly, the spherical composite material is beneficial to stabilizing the structure when being used as an electrode for charge and discharge circulation, and a buffer space is provided for volume change in the reaction process.
The thickness of the zinc vanadate (Zn 3V3O 8) nanosheets is preferably 10nm-200nm, and more preferably 10nm-100 nm; the nanoscale thickness provides negligible ion diffusion and transfer time, which is beneficial for performance enhancement of the electrochemical diffusion control process.
The preparation method of the zinc vanadate coated carbon microsphere composite material comprises the following steps:
1. preparation of carbon microspheres:
1-1, preparing glucose solution with the concentration of 0.23mol/L to 0.38mol/L in a beaker;
1-2, adding sodium hydroxide, citric acid and formaldehyde aqueous solution with the concentration of 0.37mol/L-0.40 mol/L, and fully stirring to form mixed solution; wherein, the sodium hydroxide and the citric acid have the functions of adjusting the pH value of a reaction system, and the pH value of the reaction system is preferably 8;
1-3, pouring the mixed solution into a polytetrafluoroethylene mould, and performing a hydrothermal reaction to obtain a hydrothermal reaction product, wherein the hydrothermal reaction condition is 160 ℃ for 6 hours;
1-4, alternately centrifuging the hydrothermal reaction product with deionized water and ethanol at 8000r/min, and collecting to obtain a first precipitate;
1-5, vacuum freeze-drying the collected first precipitate for 48 hours at the freezing temperature of-80 ℃ to obtain carbon microspheres;
2. preparation of zinc vanadate coated carbon microsphere composite material:
2-1, pouring glycol into a beaker;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
2-3, adding the carbon microsphere material prepared in the step (1) into the suspension, and continuously stirring until the carbon microsphere material is uniformly dispersed;
2-4, pouring the suspension into a polytetrafluoroethylene die for solvothermal reaction to obtain a solvothermal reaction product, wherein the reaction condition of the solvothermal reaction is 180 ℃ for 12 hours;
2-5, alternately centrifuging the solvothermal reaction product with deionized water and ethanol at 8000r/min, and collecting to obtain a second precipitate;
2-6, vacuum freeze-drying the collected second precipitate for 48 hours at the freezing temperature of-80 ℃;
2-7, placing the freeze-dried product into a tube furnace, and preserving heat at 400-600 ℃ in nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and the preserving heat time is 6 hours, so as to obtain the zinc vanadate nanosheet coated carbon microsphere composite material; the holding temperature is further preferably 600 ℃.
The composite material of the zinc vanadate coated carbon microsphere prepared by the method is used as a positive electrode material of a water-based zinc ion battery.
The specific application method of the zinc vanadate coated carbon microsphere composite material as the water-based zinc ion battery anode material comprises the following steps:
1. dispersing a composite material of zinc vanadate nanosheets coated with carbon microspheres, conductive carbon black and polyvinylidene fluoride in a mass ratio of 7:2:1 in N-methylpyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven at 110 ℃ for 12 hours under a vacuum condition to obtain a water-based zinc ion battery anode electrode material;
2. the obtained water-based zinc ion battery positive electrode material is cut into a round electrode with the diameter of 14 and mm, a platinum net and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, whatman GF/D glass fiber filter paper is used as a diaphragm, and the button cell is assembled.
The assembled button cell was tested by an electrochemical workstation Autolab.
According to the invention, a two-step hydrothermal method (a hydrothermal reaction in the preparation process of the carbon microsphere and a solvothermal reaction in the preparation process of the zinc vanadate coated carbon microsphere composite material) and a heat treatment method (an annealing reaction which is performed at a certain temperature and for a certain time in the nitrogen atmosphere in the preparation process of the zinc vanadate coated carbon microsphere composite material) are utilized to synthesize the zinc vanadate nano-sheet coated carbon microsphere composite material with excellent electrochemical performance; the composite material of the zinc vanadate nanosheet coated carbon microsphere prepared by the invention is used as a water-based zinc ion battery positive electrode material, and the current density is 1 Ag -1 When the specific discharge capacity reaches 300mAh g -1 The above; the composite material of the zinc vanadate coated carbon microsphere prepared by the method has a spherical morphology, and the whole preparation process is safe and simple to operate, thereby providing a novel method for preparing the zinc vanadate.
The glucose is preferably biomass glucose.
In the preparation method provided by the invention, glucose reacts in a weak alkaline environment under the condition of hydrothermal reaction to generate a spherical template-carbon microsphere; ethylene glycol is used as a solvent, ammonium metavanadate is used as a vanadium source, zinc triflate is used as a zinc source, polyvinylpyrrolidone is used as a surfactant, and carbon microspheres are used as templates, and zinc vanadate formed under the solvothermal reaction condition and the action of the surfactant is attached to the carbon microspheres to obtain a zinc vanadate/carbon microsphere precursor; carrying out high-temperature heat treatment in a nitrogen atmosphere in a tube furnace, annealing zinc vanadate attached to the carbon microsphere into a nano sheet, loosening the structure of the carbon microsphere at high temperature, and finally obtaining the zinc vanadate nano sheet-coated carbon microsphere composite material; the particle size of the carbon microsphere in the composite material of the zinc vanadate nanosheet coated carbon microsphere prepared by the preparation method can be distributed between 1 μm and 10 μm, the thickness of the zinc vanadate (Zn 3V3O 8) nanosheet can be distributed between 10nm and 200nm, and the thickness of most of zinc vanadate (Zn 3V3O 8) nanosheets can be distributed between 10nm and 100 nm.
The invention provides a positive electrode material of a water system zinc ion battery, which is characterized in that a zinc vanadate nanosheet is attached to the surface of a carbon microsphere, so that the capacity can be increased while the conductivity of the carbon microsphere coated by the zinc vanadate nanosheet is ensured; specifically, the participation of the carbon microspheres makes the electronic conduction easier, and the overall conductivity of the composite material is improved based on the electronic conduction; the contact area between the flaky structure of the zinc vanadate nano-sheet and the electrolyte is large, ions are easier to embed, and higher specific capacity can be provided in the same charge and discharge time; the zinc vanadate nanosheets are attached to the spherical templates, and the composite material is spherical, so that the volume expansion in the charge and discharge process has more selectivity in the direction compared with the plane structure, the collapse and rupture time of the structure is prolonged in the battery circulation process, the structural stability is high, and the service life of the battery is greatly prolonged; the composite material of the carbon microsphere coated by the zinc vanadate nano-sheet is used as a positive electrode material of a water-based zinc ion battery (AZIBs), and the composite material is assembled into the water-based zinc ion battery, so that the excellent electrochemical behavior is shown.
The invention will be further illustrated with reference to specific examples.
Example 1
1. Preparation of carbon microspheres:
(a) Preparing glucose solution with concentration of 0.23mol/L in a beaker;
(b) Adding sodium hydroxide, citric acid and formaldehyde aqueous solution with the concentration of 0.37mol/L, and fully stirring;
(c) Pouring the mixed solution into a polytetrafluoroethylene mould for hydrothermal reaction, wherein the reaction condition is 160 ℃ for 4 hours;
(d) Alternately centrifuging the hydrothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(e) Vacuum freeze-drying the collected precipitate for 48 hours at the temperature of-80 ℃ to obtain carbon microspheres;
2. preparation of zinc vanadate coated carbon microsphere composite material:
(a) Pouring glycol into a beaker;
(b) Uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
(c) Adding the carbon microsphere material in the step (1) into the suspension, and continuously stirring the mixture to be uniformly dispersed;
(d) Pouring the suspension into a polytetrafluoroethylene mould for solvothermal reaction under the reaction condition of 180 ℃ for 8h;
(e) Alternately centrifuging the solvothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) Vacuum freeze drying the collected precipitate for 48h at-80deg.C;
(g) And (3) placing the dried product in a tube furnace, and respectively carrying out heat preservation at 400 ℃ and a heating rate of 5 ℃/min for 6 hours in a nitrogen atmosphere to obtain the zinc vanadate nanosheet coated carbon microsphere composite material.
3. Preparation of a zinc vanadate nanosheet coated carbon microsphere composite material as an electrode material of a water-based zinc ion battery:
and (3) dispersing the composite material of the zinc vanadate nanosheet coated carbon microsphere prepared in the step (2), super P (conductive carbon black) and polyvinylidene fluoride in the mass ratio of 7:2:1 in N-methyl pyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven at 110 ℃ for 12 hours under a vacuum condition to obtain the battery anode material.
4. Test of zinc vanadate nanosheet coated carbon microsphere composite as electrode material of zinc ion battery:
cutting the battery anode material in the step 3 into a round electrode with the diameter of 14 mm, using a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode respectively, using Whatman GF/D glass fiber filter paper as a diaphragm, and assembling the button battery, wherein electrolyte in the button battery is zinc trifluoromethane sulfonate solution with the concentration of 2.8-3.0 mol/L, and the cathode is a zinc sheet; the button cell is tested by an electrochemical workstation Autolab, the current density is 0.1A/g, and the charge and discharge performance of the button cell is tested as shown in figure 8; the button cell was cycled (voltage window 0.3-1.7V) by a blue cell tester CT2001A with the rate capability shown in example 1 of fig. 11.
Taking the ultrathin zinc vanadate nanosheet coated carbon microsphere composite material prepared in the embodiment 1 as an example, the scanning electron microscope photograph of the attached figure 1 can observe that the composite material basically shows a shape with tightly combined zinc vanadate and carbon microsphere; the structure is relatively poor in crystallinity, as can be seen from XRD of FIG. 5, and no Zn is present 3 V 3 O 8 Is a characteristic peak of the whole of the characteristic peaks of (a); as can be seen from the charge and discharge test results of FIG. 8, the three-electrode test method was used as an independent electrode sheet, and the current density was 1A g -1 At the time, the specific discharge capacity was 187mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from the rate performance chart of FIG. 11, the button cell was tested by the two-electrode method at current densities of 0.1, 0.2, 0.5, 1, 2, 3, 4, 5A g, respectively, as the positive electrode active material of the aqueous zinc ion cell -1 The specific discharge capacities of the full cells were 247.8, 164.8, 126.5, 108.3, 90.0, 72.5, 60.0 and 48.6mAh g, respectively -1 And when the current density returns to the low current density (0.1A g) -1 ) The specific discharge capacity is 133.7 mAh g -1 The better electrochemical performance can be seen.
Example 2
1. Preparation of carbon microspheres:
(a) Preparing glucose solution with concentration of 0.30mol/L in a beaker;
(b) Adding sodium hydroxide, citric acid and formaldehyde aqueous solution with the concentration of 0.38mol/L, and fully stirring;
(c) Pouring the mixed solution into a polytetrafluoroethylene mould for hydrothermal reaction, wherein the reaction condition is 160 ℃ for 5h;
(d) Alternately centrifuging the hydrothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(e) Vacuum freeze-drying the collected precipitate for 48 hours at the temperature of-80 ℃ to obtain carbon microspheres;
2. preparation of zinc vanadate coated carbon microsphere composite material:
(a) Pouring glycol into a beaker;
(b) Uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
(c) Adding the carbon microsphere material in the step (1) into the suspension, and continuously stirring the mixture to be uniformly dispersed;
(d) Pouring the suspension into a polytetrafluoroethylene mould for solvothermal reaction under the reaction condition of 180 ℃ for 10h;
(e) Alternately centrifuging the solvothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) Vacuum freeze drying the collected precipitate for 48h at-80deg.C;
(g) And (3) placing the dried product in a tube furnace, and respectively carrying out heat preservation at 500 ℃ and a heating rate of 5 ℃/min for 6 hours in a nitrogen atmosphere to obtain the zinc vanadate nanosheet coated carbon microsphere composite material.
3. Preparation of a zinc vanadate nanosheet coated carbon microsphere composite material as an electrode material of a water-based zinc ion battery:
and (3) dispersing the composite material of the zinc vanadate nanosheet coated carbon microsphere prepared in the step (2), super P and polyvinylidene fluoride in the mass ratio of 7:2:1 into N-methylpyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven at 110 ℃ for 12 hours under a vacuum condition to obtain the battery anode material.
4. Test of zinc vanadate nanosheet coated carbon microsphere composite material as electrode material of zinc ion battery
Cutting the battery anode material in the step 3 into a round electrode with the diameter of 14 mm, respectively taking a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode, and taking Whatman GF/D as a diaphragm to assemble a button battery, wherein electrolyte in the button battery is zinc triflate solution with the concentration of 2.8-3.0 mol/L, and the cathode is a zinc sheet; button cell was tested by electrochemical workstation Autolab with current density of 0.1. 0.1A g -1 The charge and discharge performance of the material is tested as shown in figure 9; the button cell was cycled (voltage window 0.3-1.7V) by a blue cell tester CT2001A with the rate capability shown in example 2 of fig. 11.
Taking the ultrathin zinc vanadate nanosheet coated carbon microsphere composite material prepared in the embodiment 2 as an example, the scanning electron microscope image of the attached figure 2 can observe that the composite material basically achieves the expected morphology of the zinc vanadate coated carbon microsphere; as can be seen from XRD of FIG. 6, the crystallinity is relatively good, and the peak positions are respectively instable, but basically accord with Zn in PDF standard card 3 V 3 O 8 Is a characteristic peak of the whole of the characteristic peaks of (a); as can be seen from the charge and discharge test results of FIG. 9, the three-electrode test method was used as an independent electrode sheet, and the current density was 1A g -1 At the time of discharge, the specific discharge capacity was 213mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from the rate performance chart of FIG. 11, the button cell was tested by the two-electrode method at current densities of 0.1, 0.2, 0.5, 1, 2, 3, 4, 5A g, respectively, as the positive electrode active material of the aqueous zinc ion cell -1 The specific discharge capacities of the full cells were 286.3, 222.6, 191.7, 173.0, 133.3, 98.3, 76.7 and 59.7 mAh g, respectively -1 And when the current density returns to the low current density (0.1A g) -1 ) The specific discharge capacity of the material reaches 196.3 mAh g -1 It can be seen that the cycling performance of the battery is relatively stable, and the electrochemical performance is greatly improved compared with that of example 1.
Example 3
1. Preparation of carbon microspheres:
(a) Preparing a glucose solution with the concentration of 0.38mol/L in a beaker;
(b) Adding sodium hydroxide, citric acid and formaldehyde aqueous solution with the concentration of 0.40 mol/L, and fully stirring;
(c) Pouring the mixed solution into a polytetrafluoroethylene mould for hydrothermal reaction, wherein the reaction condition is 160 ℃ for 6 hours;
(d) Alternately centrifuging the hydrothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(e) Vacuum freeze-drying the collected precipitate for 48 hours at the temperature of-80 ℃ to obtain carbon microspheres;
2. preparation of zinc vanadate coated carbon microsphere composite material:
(a) Pouring glycol into a beaker;
(b) Uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
(c) Adding the carbon microsphere material in the step (1) into the suspension, and continuously stirring the mixture to be uniformly dispersed;
(d) Pouring the suspension into a polytetrafluoroethylene mould for solvothermal reaction under the reaction condition of 180 ℃ for 12h;
(e) Alternately centrifuging the solvothermal reaction product with deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) Vacuum freeze drying the collected precipitate for 48h at-80deg.C;
(g) And (3) placing the dried product in a tube furnace, and respectively carrying out heat preservation at 600 ℃ and a heating rate of 5 ℃/min for 6 hours in a nitrogen atmosphere to obtain the zinc vanadate nanosheet coated carbon microsphere composite material.
3. Preparation of zinc vanadate nanosheet coated carbon microsphere composite material as electrode material of water-based zinc ion battery
And (3) dispersing the composite material of the zinc vanadate nanosheet coated carbon microsphere prepared in the step (2), super P and polyvinylidene fluoride in the mass ratio of 7:2:1 into N-methylpyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven at 110 ℃ for 12 hours under a vacuum condition to obtain the battery anode material.
4. Test of zinc vanadate nanosheet coated carbon microsphere composite material as electrode material of zinc ion battery
Cutting the battery anode material in the step 3 into a round electrode with the diameter of 14 mm, respectively taking a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode, and taking Whatman GF/D as a diaphragm to assemble a button battery, wherein the electrolyte of the button battery is zinc triflate solution with the concentration of 2.8-3.0 mol/L, and the negative electrode is a zinc sheet; button cell was tested by electrochemical workstation Autolab with current density of 0.1. 0.1A g -1 The charge and discharge performance of the material is tested as shown in figure 10; the button cell was cycled (voltage window 0.3-1.7V) by a blue cell tester CT2001A, with the rate capability shown in example 3 of fig. 11.
Taking the ultrathin zinc vanadate nanosheet coated carbon microsphere composite material prepared in the embodiment 3 as an example, the composite material can be observed to be in a regular and uniform spherical shape from a scanning electron microscope image of fig. 3, and the ultrathin zinc vanadate nanosheets on the surface of the composite material and the spherical shape provided by taking the carbon microsphere as a template can be seen from a single particle detail image of fig. 4, so that the success of material synthesis is illustrated; the structure is shown in XRD of figure 7, the crystallinity is good, and the diffraction peak accords with Zn 3 V 3 O 8 Is a characteristic peak of the whole of the characteristic peaks of (a); as can be seen from the charge and discharge test results of FIG. 10, the three-electrode test method was used as an independent electrode sheet, and the current density was 1A g -1 At the time of discharge, the specific capacity was 275mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the As can be seen from the rate performance chart of FIG. 11, the button cell was tested by the two-electrode method at current densities of 0.1, 0.2, 0.5, 1, 2, 3, 4, 5A g, respectively, as the positive electrode active material of the aqueous zinc ion cell -1 The specific discharge capacities of the full cells were 312.3, 278.1, 242.3, 218.0, 183.9, 147.5, 118.9, 93.0mAh g, respectively -1 And when the current density returns to the low current density (0.1A g) -1 ) The specific discharge capacity of the material is still kept at 257.6 mAh g -1 It can be seen that it has excellent electrochemical properties.

Claims (8)

1. The composite material of the zinc vanadate coated carbon microsphere is characterized by comprising the carbon microsphere and a zinc vanadate nanosheet, wherein the carbon microsphere is coated by the zinc vanadate nanosheet;
the preparation method of the zinc vanadate coated carbon microsphere composite material comprises the following steps:
1. preparing carbon microspheres by a hydrothermal method;
2. coating the carbon microspheres by zinc vanadate nanosheets by a hydrothermal method and a heat treatment method;
the method for coating the carbon microsphere by the zinc vanadate nanosheets by using a hydrothermal method and a heat treatment method comprises the following steps:
2-1, pouring ethylene glycol into a container;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethane sulfonate and polyvinylpyrrolidone into ethylene glycol to obtain a suspension;
2-3, adding the carbon microspheres prepared by a hydrothermal method into the suspension, and continuing until the carbon microspheres are uniformly dispersed;
2-4, carrying out solvothermal reaction on the suspension dispersed with the carbon microspheres to obtain a solvothermal reaction product;
2-5, centrifuging the solvothermal reaction product, and collecting a second precipitate;
2-6, vacuum freeze-drying the collected second precipitate;
2-7, carrying out heat preservation on the dried product for a certain time at the heat preservation temperature in the nitrogen atmosphere to obtain the zinc vanadate nanosheet coated carbon microsphere composite material.
2. The zinc vanadate coated carbon microsphere composite according to claim 1, wherein the carbon microsphere has a particle size in the range of 1 μm to 10 μm.
3. The zinc vanadate coated carbon microsphere composite according to claim 1, wherein the zinc vanadate nanosheets have a thickness of 10nm-200nm.
4. The zinc vanadate coated carbon microsphere composite material according to claim 1, wherein the carbon microsphere preparation by a hydrothermal method comprises the following steps:
1-1, preparing a glucose solution;
1-2, adding a pH value regulator and a formaldehyde aqueous solution into the glucose solution, and fully stirring to form a mixed solution;
1-3, carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product;
1-4, centrifuging the hydrothermal reaction product, and collecting to obtain a first precipitate;
1-5, performing vacuum freeze drying on the collected first precipitate to obtain the carbon microsphere.
5. The zinc vanadate coated carbon microsphere composite according to claim 4, wherein the pH regulator is sodium hydroxide and citric acid, and the pH regulator is used for regulating the pH value to 8; the solubility of the glucose solution is 0.23mol/L-0.38mol/L; the concentration of the formaldehyde aqueous solution is 0.37mol/L-0.40 mol/L;
the mixed solution is subjected to hydrothermal reaction to obtain a hydrothermal reaction product, which is specifically as follows: pouring the mixed solution into a polytetrafluoroethylene mould, and performing a hydrothermal reaction to obtain a hydrothermal reaction product; the hydrothermal reaction condition is 160 ℃ for 4-6 hours;
the specific method for centrifuging the hydrothermal reaction product comprises the following steps: alternately centrifuging with deionized water and ethanol at 8000 r/min;
the first precipitate collected is freeze-dried in vacuum, and is specifically: the collected first precipitate was freeze-dried in vacuo for 48h at-80 ℃.
6. The zinc vanadate coated carbon microsphere composite material according to claim 1, wherein the concentration of sodium metavanadate in ethylene glycol is 0.10 mol/L-0.15 mol/L; the concentration of the zinc triflate in the glycol is 0.030 mol/L-0.035 mol/L; the concentration of the polyvinylpyrrolidone in the glycol is 1.55-g/L-1.70 g/L; the concentration of the carbon microsphere in the glycol is 10 g/L;
the suspension dispersed with carbon microspheres is subjected to solvothermal reaction to obtain a solvothermal reaction product, which is specifically as follows: pouring the suspension with the carbon microspheres into a polytetrafluoroethylene mould for solvothermal reaction; the reaction condition of the solvothermal reaction is 180 ℃ for 8-12 h;
the specific method for centrifuging the solvothermal reaction product comprises the following steps: alternately centrifuging with deionized water and ethanol at 8000 r/min;
the second precipitate collected is freeze-dried in vacuum, and is specifically: vacuum freeze-drying the collected second precipitate for 48h at-80 ℃;
the heat preservation temperature is 400-600 ℃; the heat preservation temperature is specifically that the temperature is raised from the room temperature to the heat preservation temperature at a heating rate of 5 ℃/min; and the heat preservation for a certain time is 6 hours.
7. The application of the zinc vanadate coated carbon microsphere composite material according to claim 1, wherein the zinc vanadate coated carbon microsphere composite material is used as a positive electrode material of a water-based zinc ion battery.
8. The use of the zinc vanadate coated carbon microsphere composite according to claim 7, characterized by comprising in particular the following: and dispersing the composite material of the zinc vanadate nanosheets coated with the carbon microspheres, the conductive carbon black and the polyvinylidene fluoride in the mass ratio of 7:2:1 in N-methylpyrrolidone to prepare slurry, coating the slurry on a Ti foil, and then drying the Ti foil in an oven under a vacuum condition to obtain the water-based zinc ion battery anode material.
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