CN114914423A - Zinc vanadate coated carbon microsphere composite material and preparation method and application thereof - Google Patents
Zinc vanadate coated carbon microsphere composite material and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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- 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
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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 preparation method of a composite material of zinc vanadate coated carbon microspheres comprises the following steps: 1. preparing carbon microspheres by a hydrothermal method; 2. coating the carbon microspheres by the zinc vanadate nanosheets by using 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
Technical Field
The invention relates to a zinc vanadate coated carbon microsphere composite material and a preparation method and application thereof, belonging to the technical field of new energy materials.
Background
With the continuous development of society and the progress of technology, electronic products are more and more popular, and energy storage becomes crucial; the traditional lithium ion battery cannot be produced and applied in large scale to meet the requirements of the energy storage market due to inherent insecurity and expensive processing cost; in recent years, water-based zinc ion batteries are popular candidates for lithium ion batteries due to the characteristics of environmental protection, high safety, large-scale development and the like.
Vanadium oxide and a complex thereof, manganese oxide and a complex thereof, prussian blue analogue, and a bimetallic compound have been hitherto most commonly used as positive electrode materials for aqueous zinc-ion batteries; the vanadium oxide has an inherent layered 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 cycling stability of pure vanadium oxide cannot be ignored, because the pure vanadium oxide has poor conductivity, is not beneficial to electron transport, and hinders electrochemical reaction, thereby affecting the rate capability; in addition, volume expansion easily occurs in the circulation process, the internal structure can rapidly collapse, capacity is rapidly attenuated, and circulation stability is poor.
Vanadium-based bimetallic oxides (e.g. Fe) 2 VO 4 、CaV 2 O 7 Etc.) have gradually come into the field of view of people in recent years due to unique structure and superior physicochemical properties, and have been widely noticed and applied to various fields of energy storage, catalysis, etc., wherein zinc vanadate has zinc-rich property and multi-electron transport property due to vanadium, and Zn has been charged for the first time 2+ Will be removed to bring extra metal vacancy to improve the capacity, so that the zinc-ion battery anode material is very suitable to be used as a water system zinc-ion battery anode material; however, the capacity provided by the zinc vanadate material as the cathode material of the water-based zinc ion battery is generally low, and the safety of the preparation process is low, so that the research on the preparation method of the zinc vanadate, which has the advantages of controllable appearance, simplicity and convenience in operation and high safety, is very meaningful on the premise of ensuring the discharge capacity.
Disclosure of Invention
The invention provides a zinc vanadate coated carbon microsphere composite material, a preparation method and application thereof, and aims to prepare a positive electrode material applicable to a water system zinc ion battery.
The technical solution of the invention is as follows: the composite material of the carbon microsphere coated by the zinc vanadate structurally comprises the carbon microsphere and zinc vanadate (Zn3V3O8) nanosheets, wherein the carbon microsphere is coated by the zinc vanadate (Zn3V3O8) nanosheets.
Further, the particle size of the carbon microsphere is preferably in the range of 1 μm to 10 μm.
Further, the thickness of the zinc vanadate (Zn3V3O8) nanosheet is preferably 10nm-200 nm.
A preparation method of a composite material of zinc vanadate coated carbon microspheres comprises the following steps:
1. preparing carbon microspheres by a hydrothermal method;
2. and coating the carbon microspheres by the zinc vanadate nanosheets by using a hydrothermal method and a heat treatment method.
Further, the hydrothermal method for preparing the carbon microsphere specifically comprises the following steps:
1-1, preparing a glucose solution;
1-2, adding a pH value regulator and a formaldehyde aqueous solution into a glucose solution, and fully stirring to form a mixed solution;
1-3, carrying out a hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product;
1-4, centrifuging a hydrothermal reaction product, and collecting to obtain a first precipitate;
1-5, and carrying out vacuum freeze drying on the collected first precipitate to obtain the carbon microsphere.
Further, the coating of the zinc vanadate nanosheets on the carbon microspheres by using a hydrothermal method and a heat treatment method specifically comprises the following steps:
2-1, pouring ethylene glycol into a container;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 to obtain a second precipitate;
2-6, carrying out vacuum freeze drying on the collected second precipitate;
and 2-7, preserving the heat of the dried product in a nitrogen atmosphere at a heat preservation temperature for a certain time to obtain the composite material of the carbon microsphere coated by the zinc vanadate nano sheet.
Further, the pH adjusting agent is preferably sodium hydroxide and citric acid, and is used for adjusting the pH to preferably 8; the solubility of the glucose solution is preferably 0.23-0.38 mol/L; the concentration of the formaldehyde aqueous solution is preferably 0.37-0.40 mol/L; the solubility of the glucose solution is further preferably 0.38 mol/L; the concentration of the aqueous formaldehyde solution is more preferably 0.40 mol/L.
Further, performing a hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product, specifically: pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction to obtain a hydrothermal reaction product; the condition of the hydrothermal reaction is preferably 160 ℃ for 4-6 h; the hydrothermal reaction condition is further preferably 160 ℃ for 6 h.
Further, the specific method for centrifuging the hydrothermal reaction product comprises the following steps: the mixture was centrifuged alternately with deionized water and ethanol at 8000 r/min.
Further, the collected first precipitate is vacuum freeze-dried, specifically: the first precipitate collected was freeze dried in vacuo for 48h at-80 ℃.
Further, the concentration of the ammonium metavanadate in the ethylene glycol is preferably 0.10 mol/L-0.15 mol/L; the concentration of the zinc trifluoromethanesulfonate in the ethylene glycol is preferably 0.030 mol/L-0.035 mol/L; the concentration of the polyvinylpyrrolidone in the glycol is preferably 1.55 g/L-1.70 g/L; the concentration of the carbon microspheres in the glycol is preferably 10 g/L.
Further, the suspension in which the carbon microspheres are dispersed is subjected to a solvothermal reaction to obtain a solvothermal reaction product, which specifically comprises: pouring the suspension dispersed with the carbon microspheres into a polytetrafluoroethylene mold to carry out solvothermal reaction; the reaction condition of the solvothermal reaction is that the reaction is carried out at 180 ℃ for 8-12 h; the reaction condition of the solvothermal reaction is further preferably 180 ℃ for 12 h.
Further, the specific method for centrifuging the solvothermal reaction product comprises the following steps: centrifuge alternately with deionized water and ethanol at 8000 r/min.
Further, the collected second precipitate is vacuum freeze-dried, specifically: the second precipitate collected was freeze dried in vacuo for 48h at-80 ℃.
Further, the heat preservation temperature is preferably 400-600 ℃; the heat preservation temperature is specifically increased from room temperature to the heat preservation temperature at the temperature increase rate of 5 ℃/min; the heat preservation is carried out for 6 hours; the incubation temperature is more 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 carbon microsphere coated by the zinc vanadate specifically comprises the following steps: and dispersing the composite material of the zinc vanadate nano sheet coated carbon microspheres, conductive carbon black and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry under the vacuum condition to obtain the water system zinc ion battery anode material.
The invention has the beneficial effects that:
the composite material of the zinc vanadate coated carbon microspheres prepared by the preparation method provided by the invention is used for the anode 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 coating the carbon microspheres with the zinc vanadate nano-sheets has a higher specific surface area, so that the contact area between an active material and an electrolyte can be increased, an ion diffusion path can be shortened, and more space can be provided for volume expansion in the charge-discharge process; in conclusion, the composite material of the zinc vanadate coated carbon microsphere prepared by the invention can effectively improve the electrochemical performance of the water system zinc ion battery.
Drawings
Fig. 1 is a scanning electron microscope photograph of the composite material in which the carbon microspheres are coated with the ultrathin zinc vanadate nanosheets prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope photograph of the composite material in which the carbon microspheres are coated with the ultrathin zinc vanadate nanosheets prepared in example 2 of the present invention.
Fig. 3 is a scanning electron micrograph of the ultra-thin zinc vanadate nanosheet coated carbon microsphere composite material prepared in example 3 of the present invention.
Fig. 4 is a scanning electron microscope photograph ii of the composite material in which the carbon microspheres are coated on the ultra-thin zinc vanadate nanosheets prepared in example 3 of the present invention.
Figure 5 is an XRD pattern of the product prepared in example 1 of the invention.
Figure 6 is an XRD pattern of the product prepared in example 2 of the present invention.
Figure 7 is an XRD pattern of the product prepared in example 3 of the present invention.
Fig. 8 is a graph of five charge and discharge tests performed on the composite material in which the ultra-thin zinc vanadate nano sheet is coated with the carbon microspheres as the positive electrode in the water-based zinc ion battery at the same current density in example 1 of the present invention.
Fig. 9 is a graph of five charge and discharge tests performed on the composite material in which the ultra-thin zinc vanadate nano sheet is coated with the carbon microspheres as the positive electrode in the water-based zinc ion battery at the same current density in example 2 of the present invention.
Fig. 10 is a graph of five charge and discharge tests performed on the composite material in which the ultra-thin zinc vanadate nanosheets are coated with the carbon microspheres, as a positive electrode, in an aqueous zinc-ion battery at the same current density in example 3 of the invention.
Fig. 11 is a graph of the rate performance of the composite material in which the ultrathin zinc vanadate nanosheets are coated with carbon microspheres in examples 1-3 of the invention as a positive electrode in an aqueous zinc ion battery.
Detailed Description
The composite material of the carbon microsphere coated with the zinc vanadate structurally comprises the carbon microsphere and zinc vanadate (Zn3V3O8) nanosheets, wherein the carbon microsphere is coated with the zinc vanadate (Zn3V3O8) nanosheets.
The particle size range of the carbon microsphere is preferably 1-10 μm, and more preferably 4-8 μm; the carbon microspheres with uniform size are used as templates to load the ultrathin vanadium acid nanosheets, controllable conditions are provided for the morphology of the composite material, and similarly, the spherical composite material is beneficial to stabilizing the structure when used as an electrode for charge-discharge circulation, and a buffer space is provided for volume change in the reaction process.
The thickness of the zinc vanadate (Zn3V3O8) nanosheet is preferably 10nm-200nm, and more preferably 10nm-100 nm; the nanoscale thickness provides negligible ion diffusion and transfer time, which is beneficial to the performance improvement of the electrochemical diffusion control process.
A preparation method of a composite material of zinc vanadate coated carbon microspheres comprises the following steps:
1. preparing carbon microspheres:
1-1, preparing a glucose solution with the concentration of 0.23-0.38 mol/L in a beaker;
1-2, adding sodium hydroxide, citric acid and 0.37-0.40 mol/L formaldehyde water solution, and fully stirring to form a mixed solution; wherein, the effect of the sodium hydroxide and the citric acid is to adjust the pH value of the reaction system, and the pH =8 of the reaction system is suitable;
1-3, pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction under the condition of 160 ℃ for 6 hours to obtain a hydrothermal reaction product;
1-4, alternately centrifuging the hydrothermal reaction product by using deionized water and ethanol at 8000r/min, and collecting to obtain a first precipitate;
1-5, carrying out vacuum freeze drying on the collected first precipitate for 48 hours at the freezing temperature of-80 ℃ to obtain carbon microspheres;
2. preparing a zinc vanadate coated carbon microsphere composite material:
2-1, pouring ethylene glycol into a beaker;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 dispersion is uniform;
2-4, pouring the suspension into a polytetrafluoroethylene mold to carry out 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 solvent thermal reaction product by using deionized water and ethanol at 8000r/min, and collecting to obtain a second precipitate;
2-6, carrying out vacuum freeze drying on the collected second precipitate for 48 hours, wherein the freezing temperature is-80 ℃;
2-7, placing the freeze-dried product in a tubular furnace, and preserving heat at 400-600 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and the heat preservation time is 6h, so as to obtain the composite material of the zinc vanadate nanosheet coated carbon microspheres; the incubation temperature is more preferably 600 ℃.
The composite material of the zinc vanadate coated carbon microsphere prepared by the invention is used as a cathode material of a water system zinc ion battery.
The specific application method of the composite material of the zinc vanadate coated carbon microsphere as the anode material of the water system zinc ion battery comprises the following steps:
1. dispersing the composite material of the zinc vanadate nano-sheet coated carbon microspheres, conductive carbon black and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry for 12 hours at 110 ℃ under a vacuum condition to obtain the anode electrode material of the water-system zinc ion battery;
2. the obtained anode material of the water system zinc ion battery is cut into a circular electrode with the diameter of 14 mm, a platinum mesh and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and Whatman GF/D glass fiber filter paper is used as a diaphragm, so that the button cell is assembled.
The assembled button cell is tested by an electrochemical workstation Autolab.
The zinc vanadate nanosheet-coated carbon microsphere composite material with excellent electrochemical performance is synthesized by a two-step hydrothermal method (hydrothermal reaction in the preparation process of carbon microspheres and solvothermal reaction in the preparation process of a zinc vanadate-coated carbon microsphere composite material) and a heat treatment method (annealing reaction at a certain temperature and for a certain time in a nitrogen atmosphere in the preparation process of the zinc vanadate-coated carbon microsphere composite material); coating the zinc vanadate nano-sheet prepared by the inventionThe composite material of the carbon microspheres is used as a positive electrode material of an aqueous zinc ion battery, and the current density is 1A g -1 The specific discharge capacity can reach 300mAh g -1 The above; the composite material of the zinc vanadate coated carbon microsphere prepared by the method has a spherical shape, and the whole preparation process is safe and simple to operate, so that a novel method is provided for preparing zinc vanadate.
The glucose is preferably glucose of biomass.
In the preparation method provided by the invention, firstly, glucose reacts in a weak alkaline environment under the condition of hydrothermal reaction to generate a spherical template, namely carbon microspheres; using ethylene glycol as a solvent, ammonium metavanadate as a vanadium source, zinc trifluoromethanesulfonate as a zinc source, polyvinylpyrrolidone as a surfactant and carbon microspheres as a template, and under the action of the surfactant and under the condition of solvothermal reaction, forming zinc vanadate to be attached to the carbon microspheres to obtain a zinc vanadate/carbon microsphere precursor; carrying out high-temperature heat treatment in a tubular furnace in nitrogen atmosphere, annealing the zinc vanadate attached to the carbon microspheres to form nano sheets, loosening the structure of the carbon microspheres at high temperature, and finally obtaining the composite material of the carbon microspheres coated with the zinc vanadate nano sheets; the particle size of the carbon microspheres in the composite material of the carbon microspheres coated by the zinc vanadate nanosheets prepared by the preparation method can be distributed between 1 mu m and 10 mu m, the thickness of the zinc vanadate (Zn3V3O8) nanosheets can be distributed between 10nm and 200nm, and the thickness of most of the zinc vanadate (Zn3V3O8) nanosheets can be distributed between 10nm and 100 nm.
The invention provides a positive electrode material of a water system zinc ion battery, wherein zinc vanadate nanosheets are attached to the surfaces of carbon microspheres, so that the capacity can be increased while the conductivity of the carbon microspheres coated by the zinc vanadate nanosheets is ensured; specifically, the participation of the carbon microspheres enables the electronic conduction to be easier, so that the overall conductivity of the composite material is improved; the contact area of the flaky structure of the zinc vanadate nanosheet and the electrolyte is large, ions are easier to embed, and higher specific capacity can be provided within the same charging and discharging time; the zinc vanadate nanosheets are attached to the spherical template, and the composite material is spherical, so that the volume expansion in the charging and discharging process has more selectivity in the direction compared with a planar structure, the time for structure collapse and rupture is prolonged in the battery circulation process, the structural stability is strong, and the service life of the battery is greatly facilitated; the composite material of carbon microspheres coated by the zinc vanadate nanosheets is used as a positive electrode material of an Aqueous Zinc Ion Battery (AZIBs), and the aqueous zinc ion battery is assembled to show excellent electrochemical behavior.
The present invention is further illustrated by the following examples.
Example 1
1. Preparing carbon microspheres:
(a) preparing a glucose solution with the concentration of 0.23mol/L in a beaker;
(b) adding sodium hydroxide, citric acid and 0.37mol/L formaldehyde aqueous solution, and fully stirring;
(c) pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction under the reaction condition of 160 ℃ for 4 hours;
(d) alternately centrifuging the hydrothermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitates;
(e) vacuum freeze drying the collected precipitate for 48h at-80 deg.C to obtain carbon microsphere;
2. preparing a zinc vanadate coated carbon microsphere composite material:
(a) pouring ethylene glycol into a beaker;
(b) uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 vigorously until the carbon microsphere material is uniformly dispersed;
(d) pouring the suspension into a polytetrafluoroethylene mold for solvothermal reaction under the reaction condition of 180 ℃ for 8 hours;
(e) alternately centrifuging the solvent thermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) vacuum freeze drying the collected precipitate for 48h at-80 deg.C;
(g) and (3) placing the dried product in a tubular furnace, and keeping the temperature at 400 ℃, the heating rate at 5 ℃/min and the heat preservation time at 6h in the nitrogen atmosphere to obtain the composite material of the zinc vanadate nanosheet coated carbon microspheres.
3. The preparation of the water system zinc ion battery electrode material by coating the zinc vanadate nano-sheet with the carbon microsphere composite material comprises the following steps:
and (3) dispersing the composite material of the carbon microspheres coated by the zinc vanadate nano-sheets, Super P (conductive carbon black) and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry for 12 hours at the temperature of 110 ℃ under the vacuum condition to obtain the battery anode material.
4. And (3) testing the zinc vanadate nano-sheet coated carbon microsphere composite material as a zinc ion battery electrode material:
cutting the battery anode material obtained in the step 3 into circular electrodes with the diameter of 14 mm, and assembling a button battery by taking a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode respectively and taking Whatman GF/D glass fiber filter paper as a diaphragm, wherein an electrolyte in the button battery is a zinc trifluoromethanesulfonate solution with the concentration of 2.8-3.0 mol/L, and a negative electrode 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; button cells were cycled through a blue cell tester CT2001A (voltage window 0.3-1.7V) with rate capability as 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, it can be observed from the scanning electron microscope photograph shown in fig. 1 that the composite material basically presents a shape formed by tightly combining zinc vanadate and carbon microspheres; the structure can be seen from XRD of figure 5, the crystallinity is relatively poor, and Zn is not appeared 3 V 3 O 8 All characteristic peaks of (a); as can be seen from the results of the charge and discharge test shown in FIG. 8, the test was performed using the three-electrode test method as the independent electrode sheet at a current density of 1A g -1 Specific discharge capacity of 187mAh g -1 (ii) a As can be seen from the rate performance graph of FIG. 11, the zinc oxide particles are used as the positive electrode active material of the aqueous zinc-ion batteryThe button cell is tested by a two-electrode method, and the current density is respectively 0.1, 0.2, 0.5, 1, 2, 3, 4 and 5A g -1 The discharge specific capacity of the full battery is 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 a small current density (0.1A g) -1 ) The specific discharge capacity of the material is 133.7 mAh g -1 And the better electrochemical performance can be seen.
Example 2
1. Preparing carbon microspheres:
(a) preparing a glucose solution with the concentration of 0.30mol/L in a beaker;
(b) adding sodium hydroxide, citric acid and 0.38mol/L formaldehyde aqueous solution, and fully stirring;
(c) pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction under the reaction condition of 160 ℃ for 5 hours;
(d) alternately centrifuging the hydrothermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitates;
(e) vacuum freeze drying the collected precipitate for 48h at-80 deg.C to obtain carbon microsphere;
2. preparing a zinc vanadate coated carbon microsphere composite material:
(a) pouring ethylene glycol into a beaker;
(b) uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 with strong force until the carbon microsphere material is uniformly dispersed;
(d) pouring the suspension into a polytetrafluoroethylene mold for solvothermal reaction under the reaction condition of 180 ℃ for 10 hours;
(e) alternately centrifuging the solvent thermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) vacuum freeze drying the collected precipitate for 48h at-80 deg.C;
(g) and (3) placing the dried product in a tubular furnace, and keeping the temperature at 500 ℃, the heating rate at 5 ℃/min and the heat preservation time at 6h in the nitrogen atmosphere to obtain the composite material of the zinc vanadate nanosheet coated carbon microspheres.
3. The preparation of the water system zinc ion battery electrode material by coating the zinc vanadate nano-sheet with the carbon microsphere composite material comprises the following steps:
and (3) dispersing the composite material of the carbon microspheres coated by the zinc vanadate nanosheets prepared in the step (2), Super P and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry for 12 hours at the temperature of 110 ℃ under the vacuum condition to obtain the battery cathode material.
4. Test of zinc vanadate nano-sheet coated carbon microsphere composite material as zinc ion battery electrode material
Cutting the battery anode material obtained in the step 3 into a circular electrode with the diameter of 14 mm, assembling a button battery by taking a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode respectively and taking Whatman GF/D as a diaphragm, wherein an electrolyte in the button battery is a zinc trifluoromethanesulfonate solution with the concentration of 2.8-3.0 mol/L, and a negative electrode is a zinc sheet; the button cell is tested by an electrochemical workstation Autolab and has a current density of 0.1A g -1 Testing the charging and discharging performance of the alloy as shown in figure 9; button cells were tested cyclically (voltage window 0.3-1.7V) using a blue cell tester CT2001A, and the rate performance was as shown in fig. 11, example 2.
Taking the ultrathin zinc vanadate nanosheet-coated carbon microsphere composite material prepared in the embodiment 2 as an example, it can be observed from the scanning electron microscope image shown in fig. 2 that the composite material basically achieves the expected morphology of the zinc vanadate-coated carbon microsphere; the structure of the material can be seen from XRD shown in figure 6, the crystallinity is relatively good, and although the peak position has individual instability, the material basically conforms to Zn in PDF standard cards 3 V 3 O 8 All characteristic peaks of (a); as can be seen from the results of the charge and discharge test shown in FIG. 9, the three-electrode test method was used as an independent electrode sheet and the current density was 1A g -1 Specific discharge capacity of 213mAh g -1 (ii) a As can be seen from the rate performance graph of FIG. 11, when used as the positive electrode active material of the aqueous zinc-ion battery, the method uses two electrodesThe button cell is tested by the method, and the current density is respectively 0.1, 0.2, 0.5, 1, 2, 3, 4 and 5A g -1 The discharge specific capacities of the whole batteries are 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 a small current density (0.1A g) -1 ) The specific discharge capacity reaches 196.3 mAh g -1 It can be seen that the cycle performance of the battery is relatively stable, and the electrochemical performance is greatly improved compared with that of the battery in example 1.
Example 3
1. Preparing carbon microspheres:
(a) preparing a glucose solution with the concentration of 0.38mol/L in a beaker;
(b) adding sodium hydroxide, citric acid and 0.40 mol/L formaldehyde aqueous solution, and fully stirring;
(c) pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction under the reaction condition of 160 ℃ for 6 hours;
(d) alternately centrifuging the hydrothermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitates;
(e) vacuum freeze drying the collected precipitate for 48h at-80 deg.C to obtain carbon microsphere;
2. preparing a zinc vanadate coated carbon microsphere composite material:
(a) pouring ethylene glycol into a beaker;
(b) uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 vigorously until the carbon microsphere material is uniformly dispersed;
(d) pouring the suspension into a polytetrafluoroethylene mold for solvothermal reaction under the reaction condition of 180 ℃ for 12 hours;
(e) alternately centrifuging the solvent thermal reaction product by using deionized water and ethanol at 8000r/min, and collecting precipitate;
(f) vacuum freeze drying the collected precipitate for 48h at-80 deg.C;
(g) and (3) placing the dried product in a tube furnace, and keeping the temperature at 600 ℃, the heating rate at 5 ℃/min and the heat preservation time at 6h in the nitrogen atmosphere to obtain the composite material of the carbon microsphere coated by the zinc vanadate nanosheet.
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 carbon microspheres coated by the zinc vanadate nanosheets prepared in the step (2), Super P and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry for 12 hours at the temperature of 110 ℃ under the vacuum condition to obtain the battery cathode material.
4. Test of zinc vanadate nano-sheet coated carbon microsphere composite material as zinc ion battery electrode material
Cutting the battery anode material obtained in the step 3 into circular electrodes with the diameter of 14 mm, and assembling a button battery by taking a platinum mesh and a saturated calomel electrode as a counter electrode and a reference electrode respectively and taking Whatman GF/D as a diaphragm, wherein the electrolyte of the button battery is a zinc trifluoromethanesulfonate solution with the concentration of 2.8-3.0 mol/L, and the cathode of the button battery is a zinc sheet; the button cell is tested by an electrochemical workstation Autolab and has a current density of 0.1A g -1 Testing the charging and discharging performance of the alloy as shown in the attached figure 10; button cells were tested cyclically (voltage window 0.3-1.7V) using a blue cell tester CT2001A, and the rate capability was as shown in fig. 11, example 3.
Taking the carbon microsphere composite coated with the ultrathin zinc vanadate nanosheets prepared in the embodiment 3 as an example, the scanning electron microscope image in the attached drawing 3 can observe that the composite material is in a regular and uniform-size spherical shape, and the single particle detail image in the attached drawing 4 can show that the ultrathin zinc vanadate nanosheets on the surface of the composite material and the spherical shape provided by the carbon microspheres as templates show that the material is successfully synthesized; the structure can be seen from XRD shown in figure 7, the crystallinity is good, and the diffraction peak accords with Zn 3 V 3 O 8 All characteristic peaks of (a); as can be seen from the results of the charge and discharge test shown in FIG. 10, the test was carried out using the three-electrode test method as an independent electrode sheet at a current density of 1A g -1 The specific discharge capacity is 275mAh g -1 (ii) a As can be seen from the rate performance graph of fig. 11, when the active material is used as the positive electrode active material of the water-based zinc-ion battery, the button cell is tested by using a two-electrode method, and the current densities of the button cell are respectively 0.1, 0.2, 0.5, 1, 2, 3, 4 and 5A g -1 The discharge specific capacities of the whole batteries are 312.3, 278.1, 242.3, 218.0, 183.9, 147.5, 118.9 and 93.0mAh g respectively -1 And when the current density returns to a small 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 its excellent electrochemical performance.
Claims (10)
1. A composite material of carbon microspheres coated by zinc vanadate is characterized by comprising the carbon microspheres and zinc vanadate nanosheets, wherein the carbon microspheres are coated by the zinc vanadate nanosheets.
2. The composite material of claim 1, wherein the particle size of the carbon microsphere is in the range of 1 μm to 10 μm.
3. The composite material of claim 1, wherein the thickness of the zinc vanadate nano sheet is 10nm to 200 nm.
4. A preparation method of a composite material of zinc vanadate coated carbon microspheres is characterized by comprising the following steps:
1. preparing carbon microspheres by a hydrothermal method;
2. and coating the carbon microspheres by the zinc vanadate nanosheets by using a hydrothermal method and a heat treatment method.
5. The method for preparing a composite material of zinc vanadate-coated carbon microsphere according to claim 4, wherein the hydrothermal method is used for preparing the carbon microsphere, and the 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 a glucose solution, and fully stirring to form a mixed solution;
1-3, carrying out a hydrothermal reaction on the mixed solution to obtain a hydrothermal reaction product;
1-4, centrifuging a hydrothermal reaction product, and collecting to obtain a first precipitate;
1-5, and carrying out vacuum freeze drying on the collected first precipitate to obtain the carbon microsphere.
6. The method for preparing a composite material of zinc vanadate coated carbon microspheres according to claim 4, wherein the coating of the carbon microspheres by zinc vanadate nanosheets is realized by a hydrothermal method and a heat treatment method, and the method specifically comprises the following steps:
2-1, pouring ethylene glycol into a container;
2-2, uniformly dispersing sodium metavanadate, zinc trifluoromethanesulfonate 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 to obtain a second precipitate;
2-6, carrying out vacuum freeze drying on the collected second precipitate;
and 2-7, preserving the heat of the dried product in a nitrogen atmosphere at a heat preservation temperature for a certain time to obtain the composite material of the carbon microsphere coated by the zinc vanadate nano sheet.
7. The method for preparing a composite material of zinc vanadate coated carbon microspheres according to claim 5, wherein the pH value regulator is sodium hydroxide and citric acid, and is used for regulating the pH value to 8; the solubility of the glucose solution is 0.23-0.38 mol/L; the concentration of the formaldehyde aqueous solution is 0.37-0.40 mol/L;
the mixed solution is subjected to hydrothermal reaction to obtain a hydrothermal reaction product, which specifically comprises the following steps: pouring the mixed solution into a polytetrafluoroethylene mold, and carrying out hydrothermal reaction to obtain a hydrothermal reaction product; the hydrothermal reaction condition is that the reaction is carried out at 160 ℃ for 4h-6 h;
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 collected first precipitate is subjected to vacuum freeze drying, and the method specifically comprises the following steps: the first precipitate collected was freeze dried in vacuo for 48h at-80 ℃.
8. The method for preparing a composite material of zinc vanadate coated carbon microspheres according to claim 6, wherein the concentration of the ammonium metavanadate in the ethylene glycol is 0.10 mol/L-0.15 mol/L; the concentration of the zinc trifluoromethanesulfonate in the ethylene 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 microspheres in the ethylene glycol is 10 g/L;
the method comprises the following steps of carrying out solvothermal reaction on turbid liquid dispersed with carbon microspheres to obtain a solvothermal reaction product: pouring the suspension dispersed with the carbon microspheres into a polytetrafluoroethylene mold to carry out solvothermal reaction; the reaction condition of the solvothermal reaction is that the reaction is carried out at 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;
and the second precipitate is subjected to vacuum freeze drying, and specifically comprises the following steps: vacuum freeze-drying the collected second precipitate for 48h at-80 deg.C;
the heat preservation temperature is 400-600 ℃; the heat preservation temperature is specifically increased from room temperature to the heat preservation temperature at the temperature increase rate of 5 ℃/min; and the heat preservation is carried out for 6 hours.
9. The application of the composite material of the zinc vanadate coated carbon microsphere is characterized in that the composite material of the zinc vanadate coated carbon microsphere is used as a cathode material of a water system zinc ion battery.
10. The application of the composite material of the zinc vanadate coated carbon microsphere according to claim 9, which is characterized by comprising the following specific components in percentage by weight: and dispersing the composite material of the zinc vanadate nano sheet coated carbon microspheres, conductive carbon black and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7: 2: 1 to prepare slurry, coating the slurry on a Ti foil, and then placing the Ti foil in an oven to dry under the vacuum condition to obtain the water system zinc ion battery anode material.
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