CN110474044B - High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof - Google Patents

High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof Download PDF

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CN110474044B
CN110474044B CN201910840541.8A CN201910840541A CN110474044B CN 110474044 B CN110474044 B CN 110474044B CN 201910840541 A CN201910840541 A CN 201910840541A CN 110474044 B CN110474044 B CN 110474044B
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王书华
杜敏
桑元华
王建军
刘宏
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Shandong University
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Abstract

The invention provides a high-performance water-based zinc ion battery positive electrode material and a preparation method and application thereof. The cathode material has the following general formula: (N, M)Σ＝1V8O20·nH2O, wherein N is one of Li, Na, K, Zn, Cu, Mg or Ca, M is one of Mn, Fe, Co or Ni, and N is 0.01-4. The anode material can be prepared by a one-step hydrothermal method, the reaction condition is mild, the preparation process is simple, and the requirement on equipment is low; the obtained positive electrode material has a nano-belt in a microscopic shape; the obtained cathode material is applied to a water system zinc ion battery for the first time, and has electrochemical properties such as higher specific discharge capacity, higher cycling stability and the like.

Description

High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to a high-performance water-based zinc ion battery positive electrode material and a preparation method and application thereof, belonging to the technical field of zinc ion batteries.
Background
With the development of economy and society, the demand for high capacity, long life and high safety batteries is more urgent, and a high capacity battery with longer working time and higher safety is required in both portable electronic devices and electric vehicles.
Among various batteries, zinc ion batteries have high theoretical capacity (820mAh g) with zinc as the negative electrode of the battery-1) The electrolyte has the advantages of low oxidation-reduction potential, low cost and abundant reserves, and meanwhile, the water system electrolyte replaces the organic electrolyte to further reduce the pollution to the environment and is safer. At present, a major challenge facing zinc ion batteries is to find a positive electrode material that can maintain structural stability during zinc ion intercalation/deintercalation and has a high capacity.
At present, zinc ion anode materials with high capacity are mainly manganese-based materials and vanadium-based materials. Although the manganese-based material has rich resources and low cost, the manganese-based material has poor conductivity, large volume change and Mn (OH) generation in the charging and discharging processes2And Zn (OH)2By-products, which in turn lead to a doubling thereofPoor rate performance and short cycle life, which hinders further development. Vanadium-based materials have received much attention because of their low cost and their layered structure that facilitates the de-intercalation of zinc ions. Although vanadium-based materials have high capacity, most of vanadium-based materials have stability to be further improved when used as a positive electrode material for a zinc battery. Vanadium compounds currently used in aqueous zinc batteries contain V2O5，VO2，NaV3O8·1.5H2O，LiV3O8，Na2V6O16·1.63H2O，Fe5V15O39(OH)9·9H2O， Zn3V2O7(OH)2·2H2And O. In the prior art, the stability and capacity of the vanadium pentoxide as a positive electrode material of a zinc ion battery are improved by embedding metal cations into the vanadium pentoxide. Such as Zn0.25V2O5·nH2O[1]At a current density of 0.05A/g, the capacity is 300mAh g-1；Na0.33V2O5 [2]At a current density of 0.2A/g, the capacity was 253.7mAh g-1； Ca0.25V2O5·nH2O[3]At a current density of 0.05A/g, the capacity is 340mAh g-1. However, the electrochemical performance of the material used as the positive electrode material of the zinc ion battery is still to be improved.
In general, the development of new cathode materials is still the key to improve the performance of aqueous zinc batteries, and has a profound influence on the future practical application of the zinc batteries. At present, for NaV8O20The series of compounds have not been reported as a positive electrode material of an aqueous zinc ion battery.
Disclosure of Invention
The invention provides a high-performance water-based zinc ion battery positive electrode material and a preparation method and application thereof. The preparation method is simple, and the obtained positive electrode material has a nano-belt in a micro-morphology; the obtained positive electrode material is applied to a water system zinc ion battery, and has electrochemical properties such as higher specific discharge capacity, higher cycling stability and the like.
The technical scheme of the invention is as follows:
a high-performance water-based zinc ion battery positive electrode material has the following general formula: (N, M)∑＝1V8O20·nH2O, wherein N is one of Li, Na, K, Zn, Cu, Mg or Ca, M is one of Mn, Fe, Co or Ni, and N is 0.01-4. In the above general formula, "Σ ═ 1" means that the total number of atoms of the metal elements N and M is 1.
According to the invention, N in the general formula is preferably one of Na, K, Li, Zn or Ca.
According to the invention, the micro-topography of the cathode material is a nano-belt, the length of the nano-belt is 0.2-1.5 μm, and the width of the nano-belt is 60-120 nm.
The preparation method of the high-performance water-based zinc ion battery positive electrode material comprises the following steps:
weighing V2O5Fully dispersing the water-soluble salt of the metal N and the water-soluble salt of the metal M in water to obtain a mixed solution; adjusting the pH of the mixed solution to 1-4 by using an acetic acid aqueous solution; then carrying out hydrothermal reaction for 12-72h at the temperature of 90-200 ℃; centrifuging or filtering, washing and drying to obtain the anode material of the water-based zinc ion battery; m in the metal M and N in the metal N have the same meanings as M, N in the general formula of the positive electrode material, wherein M is one of Mn, Fe, Co or Ni, and N is one of Li, Na, K, Zn, Mg, Cu or Ca.
According to a preferred embodiment of the invention, the water-soluble salt of metal N is a sulfate, nitrate or chloride salt of metal N; the water-soluble salt of the metal M is a sulfate or nitrate of the metal M.
Preferably, according to the invention, N is one of Na, K, Li, Zn or Ca.
According to the invention, preferably, the water-soluble salt of the metal M is weighed according to the molar ratio of the metal M element, the vanadium element and the metal N element of 0.5-25: 0.5-15: 7, and V2O5Water-soluble salts of metal N; preferably, the water-soluble salt of the metal M is weighed according to the molar ratio of the metal M element, the vanadium element and the metal N element of 1-20:1-13:7, and V2O5And a water-soluble salt of metal N.
Preferred according to the inventionIn the mixed solution, V2O5The concentration of (b) is 0.1mol/L to 0.7 mol/L.
According to the invention, the mass fraction of the acetic acid aqueous solution is preferably 36-38%.
According to the invention, the hydrothermal reaction temperature is preferably 120-190 ℃, and the reaction time is preferably 24-72 h; preferably, the hydrothermal reaction temperature is 180 ℃ and the reaction time is 72 h.
According to the invention, the washing is preferably deionized water or absolute ethyl alcohol.
Preferably according to the invention, the drying is a vacuum drying at 40-90 ℃ for 8-20 h; preferably, the drying is carried out under vacuum at 60 ℃ for 12 h. The drying temperature needs to be proper, and the structure of the anode material can be damaged when the drying temperature is too high, so that the electrochemical performance of the anode material is greatly reduced.
The application of the high-performance water-system zinc-ion battery positive electrode material is used as a positive electrode material to be applied to a rechargeable water-system zinc-ion battery.
According to the invention, the application of the anode material in the preparation of the rechargeable aqueous zinc ion battery can be carried out according to the prior art; preferably, the application of the positive electrode material in preparing the rechargeable aqueous zinc-ion battery comprises the following steps:
(1) preparation of positive electrode plate
Uniformly mixing a positive electrode material, active carbon and polyvinylidene fluoride (PVDF) dissolved in N-methyl pyrrolidone to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, wherein the coating thickness is 200-600 mu m, and drying to obtain a positive electrode plate; the mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7: 1.5;
(2) preparation of negative electrode plate
The negative electrode is zinc foil with the thickness of 20-100 mu m, and the negative electrode slice is prepared by grinding, removing an oxidation layer, washing with ethanol and drying;
(3) preparation of the electrolyte
Dissolving zinc trifluoromethanesulfonate in deionized water to prepare electrolyte; the concentration of zinc trifluoromethanesulfonate in the electrolyte is 0.2-1.5 g/mL;
(4) preparation of the Battery
And placing the electrode plates into a battery case, placing a glass fiber diaphragm between the positive electrode plate and the negative electrode plate for separation, adding 50-80 mu L of electrolyte, and packaging the battery to obtain the rechargeable aqueous zinc ion battery.
According to the invention, in step (1), the amount of N-methylpyrrolidone added is as per the prior art.
The invention has the technical characteristics and beneficial effects that:
1. the preparation method of the cathode material is simple, and the final cathode material can be prepared only by carrying out simple hydrothermal reaction and controlling the reaction time, the reaction temperature and the drying temperature; the invention has mild reaction conditions, simple preparation process and low requirement on equipment; the obtained anode material has a specific structure, and the micro-morphology is a nanobelt.
2. The cathode raw material used by the water-based zinc ion battery is rich and the price is low; the electrolyte is zinc trifluoromethanesulfonate, so that the growth of negative dendrites is better inhibited compared with alkaline electrolyte, and high coulombic efficiency can be ensured. The zinc ion battery prepared by the anode material has higher first discharge specific capacity and cycling stability, and has better rate performance; the first discharge specific capacity can reach 350mAh g under the current density of 0.1A/g-1The above; under the current density of 4A/g, the discharge specific capacity retention rate can reach 98% after 1000 cycles.
3. The invention is to NaV8O20、KV8O20、LiV8O20The series of compounds are doped with metal cation M ions, the phase structures of the compounds are not obviously changed by doping the metal cation M ions, the interlayer spacing of the crystal structure is enlarged by doping the metal cation M ions, the zinc ions are favorably embedded, and the metal cation M ions serve as pillars between the layers, so that the structural stability of the material in the charging and discharging processes is improved, high capacity and high cycle stability are realized, and the positive electrode material with application prospect is provided for the application of a future water system zinc battery.
Drawings
FIG. 1 shows the positive electrode material of zinc ion battery prepared in example 1(Na，Mn)∑＝1V8O20·nH2X-ray diffraction (XRD) pattern of O.
FIG. 2 shows the positive electrode material (Na, Mn) of the zinc-ion battery prepared in example 1∑＝1V8O20·nH2Scanning Electron Microscope (SEM) image of O.
FIG. 3 shows the positive electrode material (Na, Mn) of the zinc-ion battery prepared in example 1∑＝1V8O20·nH2Initial charge and discharge curves of O at constant current of 0.1A/g.
FIG. 4 shows the positive electrode material (Na, Mn) of the zinc-ion battery prepared in example 1∑＝1V8O20·nH2Cycle performance diagram of O at constant current of 4A/g.
FIG. 5 shows the positive electrode material (K, Mn) of the zinc-ion battery prepared in example 5∑＝1V8O20·nH2Cycle performance diagram of O at constant current of 4A/g.
FIG. 6 shows a positive electrode material (Li, Mn) for a zinc-ion battery prepared in example 6∑＝1V8O20·nH2Cycle performance diagram of O at constant current of 4A/g.
FIG. 7 shows a positive electrode material (Zn, Mn) for a zinc-ion battery prepared in example 7∑＝1V8O20·nH2Cycle performance diagram of O at constant current of 4A/g.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
Example 1
High-performance anode material (Na, Mn) of aqueous zinc ion battery∑＝1V8O20·0.04H2A method for producing O, comprising the steps of:
according to the manganese element: vanadium element: weighing manganese sulfate, vanadium pentoxide and sodium sulfate according to the molar ratio of sodium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 37 percent of acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The application of the obtained cathode material in preparing the rechargeable aqueous zinc ion battery comprises the following steps:
(1) preparation of positive electrode plate
Uniformly mixing the prepared positive electrode material, activated carbon and polyvinylidene fluoride (PVDF) dissolved in N-methyl pyrrolidone to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, wherein the coating thickness is 400-600 mu m, and drying to obtain a positive electrode plate; the mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7: 1.5;
(2) preparation of negative electrode plate
The negative electrode is zinc foil with the thickness of 20 mu m, an oxide layer is removed by polishing with sand paper, and then the negative electrode is cleaned by ethanol and dried to obtain the negative electrode slice.
(3) Preparation of the electrolyte
5.4g of zinc trifluoromethanesulfonate was weighed and dissolved in 5ml of deionized water to prepare an electrolyte.
(4) Preparation of the Battery
And placing the electrode plates into a battery shell, placing a glass fiber diaphragm between the positive electrode plate and the negative electrode plate for separation, adding 80 mu L of electrolyte, and packaging the battery to obtain the rechargeable aqueous zinc ion battery.
The positive electrode material for zinc-ion battery prepared in this example had an X-ray diffraction (XRD) pattern as shown in FIG. 1, and its structure was (Na, Mn) by XRD analysis∑＝1V8O20·nH2O, positive electrode material of zinc ion battery prepared in this example compared with NaV8O20The phase change is not very large and the individual interplanar spacing will change slightlyAnd (6) changing.
The Scanning Electron Microscope (SEM) image of the positive electrode material of the zinc ion battery prepared in this example is shown in fig. 2, and it can be seen that the obtained positive electrode material has a micro-morphology of nanobelts, a length of 0.3-1 μm, and a width of 80-100 nm.
The first-turn charge-discharge curve of the zinc ion battery assembled by the positive electrode material of the zinc ion battery prepared in the embodiment under the constant current of 0.1A/g is shown in fig. 3, and the first-turn specific discharge capacity is 353.9mAh g by calculating the mass of the active substance of the positive electrode material-1The positive electrode material has larger specific capacity when being applied to the zinc ion battery.
The cycle performance diagram of the zinc ion battery assembled by the positive electrode material of the zinc ion battery prepared in the embodiment under the constant current of 4A/g is shown in fig. 4, and the initial specific discharge capacity is 145.9mAh g-1After 500 cycles, the discharge specific capacity retention rate is 95%; after 1000 cycles, the capacity retention rate is 86%, and the coulombic efficiency is always maintained at about 100%; the positive electrode material has better cycle stability when being applied to the zinc ion battery.
The zinc ion battery assembled by the positive electrode material of the zinc ion battery prepared by the embodiment has good rate capability, and the specific discharge capacity is 353.9mAh g under the current density of 0.1A/g-1Discharge specific capacity at a current density of 0.2A/g of 329mAh g-1Discharge specific capacity at a current density of 0.5A/g of 290mAh g-1The specific discharge capacity at a current density of 1A/g is 250mAh g-1Discharge specific capacity at a current density of 2A/g of 205mAh g-1The specific discharge capacity at a current density of 4A/g is 145.9mAh g-1。
Example 2
High-performance anode material (Na, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
according to the manganese element: vanadium element: weighing manganese sulfate, vanadium pentoxide and sodium sulfate at a molar ratio of sodium element of 1: 7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 36 mass percent acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
The positive electrode material obtained in the embodiment also shows high specific discharge capacity and cycling stability, under the current density of 4A/g, the initial specific discharge capacity is 149.5mAh g < -1 >, the capacity is kept 98% after 500 cycles, and the capacity retention rate is 91% after 1000 cycles.
The rate capability of the cathode material obtained in the embodiment is good, and the discharge specific capacity is 358.4mAh g at the current density of 0.1A/g-1The discharge specific capacity at a current density of 0.2A/g is 312mAh g-1The specific discharge capacity at a current density of 0.5A/g is 273mAh g-1Discharge specific capacity at a current density of 1A/g of 241mAh g-1The specific discharge capacity at a current density of 2A/g is 199mAh g-1The specific discharge capacity at a current density of 4A/g was 149.5mAh g-1。
Example 3
High-performance anode material (Na, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and sodium sulfate according to the molar ratio of manganese element to vanadium element to sodium element of 20: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. Adjusting the pH to 2.5 by using 38% acetic acid aqueous solution by mass fraction. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
The cathode material obtained in the embodiment has high specific discharge capacity and high cycling stability, and the initial specific discharge capacity is 151mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles is 99%, and the capacity retention rate after 1000 cycles is still as high as 98%.
The cathode material obtained in the embodiment has good rate capability, and the discharge specific capacity is 351.2mAh g at the current density of 0.1A/g-1The specific discharge capacity at a current density of 0.2A/g is 318mAh g-1The specific discharge capacity at a current density of 0.5A/g is 286mAh g-1Discharge specific capacity of 247mAh g at a current density of 1A/g-1The specific discharge capacity at a current density of 2A/g is 202mAh g-1Discharge specific capacity of 151mAh g at a current density of 4A/g-1。
Positive electrode Material (Na, Mn) of the present invention∑＝1V8O20·nH2O, different Mn doping amounts do not change greatly for capacity, and the stability in the charge-discharge cycle process is mainly improved. Because Mn is doped as a pillar of the crystal structure, the structural stability during charge-discharge cycles is improved.
Example 4
High-performance anode material (K, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and potassium sulfate according to the molar ratio of manganese element to vanadium element to potassium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 36 mass percent acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (K, Mn) of Zinc ion Battery prepared in this example∑＝1V8O20·nH2The cyclic performance diagram of O under the constant current of 4A/g is shown in figure 5, which shows that the O has very high specific discharge capacity and cyclic stability, and under the current density of 4A/g, the initial specific discharge capacity is 84.2mAh g-1And the specific discharge capacity after 500 times of circulation is 145.8mAh g-1The material has an activation process at the initial stage of charge and discharge, so that the capacity is improved, and the specific discharge capacity is 142.3mAh g after 1000 cycles-1。
The positive electrode material of the zinc ion battery prepared by the embodiment has good rate capability, and the discharge specific capacity is 301.6mAh g under the current density of 0.1A/g-1Discharge specific capacity of 278mAh g at a current density of 0.2A/g-1The specific discharge capacity at a current density of 0.5A/g was 231mAh g-1The specific discharge capacity at a current density of 1A/g is 202mAh g-1The specific discharge capacity at a current density of 2A/g is 177mAh g-1The specific discharge capacity at a current density of 4A/g is 140mAh g-1。
Example 5
High-performance anode material (Li, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and lithium sulfate according to the molar ratio of manganese element to vanadium element to lithium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 36 mass percent acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Li, Mn) for Zinc-ion Battery prepared in this example∑＝1V8O20·nH2The cycle performance diagram of O under the constant current of 4A/g is shown in figure 6, which shows that the O has very high specific discharge capacity and cycle stability, and under the current density of 4A/g, the initial specific discharge capacity is 143.4mAh g-1The capacity retention rate after 500 cycles was 85%, and the capacity retention rate after 1000 cycles was 77%.
The positive electrode material of the zinc ion battery prepared by the embodiment has good rate capability, and the discharge specific capacity is 345.3mAh g under the current density of 0.1A/g-1Discharge specific capacity at a current density of 0.2A/g of 309mAh g-1Discharge specific capacity of 271mAh g at a current density of 0.5A/g-1Discharge specific capacity at a current density of 1A/g of 236mAh g-1Discharge specific capacity at a current density of 2A/g of 194mAh g-1The specific discharge capacity at a current density of 4A/g is 143.4mAh g-1。
Example 6
High-performance aqueous zinc ion battery positive electrode material (Zn, Mn)∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and zinc sulfate according to the molar ratio of manganese element to vanadium element to zinc element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH was adjusted to 2.5 with an aqueous solution of acetic acid having a mass concentration of 36%. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Zn, Mn) of Zinc ion Battery prepared in this example∑＝1V8O20·nH2The cycle performance diagram of O under the constant current of 4A/g is shown in figure 7, and the diagram shows that the O has very high specific discharge capacity and cycle stability, and under the current density of 4A/g, the initial specific discharge capacity is 144.6mAh g-1The capacity retention rate after 500 cycles was 95%, and the capacity retention rate after 1000 cycles was 90%.
The positive electrode material of the zinc ion battery prepared by the embodiment has good rate capability, and the discharge specific capacity is 357.7mAh g under the current density of 0.1A/g-1The discharge specific capacity at a current density of 0.2A/g is 323mAh g-1The specific discharge capacity at a current density of 0.5A/g was 279mAh g-1The specific discharge capacity at a current density of 1A/g is 243mAh g-1The specific discharge capacity at a current density of 2A/g is 211mAh g-1The specific discharge capacity at a current density of 4A/g is 144.6mAh g-1。
Example 7
High-performance anode material (Ca, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and calcium chloride or calcium nitrate according to the molar ratio of manganese element to vanadium element to calcium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH was adjusted to 2.5 with an aqueous solution of acetic acid having a mass concentration of 36%. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Ca, Mn) for Zinc ion Battery prepared in this example∑＝1V8O20·nH2The initial specific discharge capacity of O is 127.9mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles was 97%.
Example 8
High-performance anode material (Na, Fe) of water-based zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing ferric sulfate, vanadium pentoxide and sodium sulfate according to the molar ratio of the iron element to the vanadium element to the sodium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH was adjusted to 2.5 with an aqueous solution of acetic acid having a mass concentration of 36%. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Na, Fe) of Zinc-ion Battery prepared in this example∑＝1VaO20·nH2The initial specific discharge capacity of O is 149.3mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles was 91%.
Example 9
High-performance anode material (Na, Co) of water-based zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing cobalt nitrate, vanadium pentoxide and sodium sulfate according to the molar ratio of cobalt element to vanadium element to sodium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH was adjusted to 2.5 with an aqueous solution of acetic acid having a mass concentration of 36%. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Na, Co) of Zinc-ion Battery prepared in this example∑＝1V8O20·nH2The initial specific discharge capacity of O is 165.2mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles was 90%.
Example 10
High-performance anode material (Na, Ni) of water-based zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing nickel sulfate, vanadium pentoxide and sodium sulfate according to the molar ratio of nickel element to vanadium element to sodium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH was adjusted to 2.5 with an aqueous solution of acetic acid having a mass concentration of 36%. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
Positive electrode Material (Na, Ni) for Zinc-ion Battery prepared in this example∑＝1V8O20·nH2O has initial discharge specific capacity of 179mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles was 88%.
Comparative example 1
Cathode material NaV of water-based zinc ion battery8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing vanadium pentoxide and sodium sulfate according to the molar ratio of vanadium element to sodium element of 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 37 percent of acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 60 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
The positive electrode material NaV of the zinc ion battery prepared by the comparative example8O20·nH2The O battery has poor performance, and the initial discharge specific capacity is 125mAh g under the current density of 4A/g-1The capacity retention rate after 500 cycles was 75%, and the capacity retention rate after 1000 cycles was only 69%. The rate capability is general, and the discharge specific capacity is 308mAh g at the current density of 0.1A/g-1The specific discharge capacity at a current density of 0.2A/g was 269mAh g-1And a specific discharge capacity of 237mAh g at a current density of 0.5A/g-1Discharge specific capacity at a current density of 1A/g of 203mAh g-1Discharge specific capacity at a current density of 2A/g of 147mAh g-1The specific discharge capacity at a current density of 4A/g is 125mAh g-1。
By comparison, NaV8O20·nH2The stability, capacity and rate capability of O are not as good as in inventive example 1. Because of NaV8O20·nH2O in the process of charging and dischargingThe poor stability, capacity and the like of Na due to the dissolution phenomenon of Na, and the stability and capacity of a crystal structure in the charging and discharging processes are improved by doping Mn in the embodiment 1 of the invention.
Comparative example 2
High-performance anode material (Na, Mn) of aqueous zinc ion battery∑＝1V8O20·nH2A process for the preparation of O (n is 0.01 to 4), comprising the steps of:
weighing manganese sulfate, vanadium pentoxide and sodium sulfate according to the molar ratio of manganese element to vanadium element to sodium element of 1: 13:7, fully dispersing the weighed raw materials in 50mL of water, and stirring for 30min to obtain a mixed solution; the mass concentration of vanadium pentoxide in the mixed solution is 0.55 mol/L. The pH value is adjusted to 2.5 by using 37 percent of acetic acid aqueous solution. Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, carrying out hydrothermal reaction for 72h at 180 ℃, carrying out centrifugal separation on precipitates after the hydrothermal reaction, washing with absolute ethyl alcohol, and carrying out vacuum drying for 12h at 120 ℃ to obtain the positive electrode material of the zinc ion battery.
The obtained cathode material is applied to the preparation of a rechargeable aqueous zinc ion battery, and the steps are as described in example 1.
The positive electrode material obtained by the comparative example has poor battery performance, and the initial specific discharge capacity is 140mAh g under the current density of 4A/g-1The capacity is kept at 50% after 500 cycles, and the capacity retention rate is 20% after 1000 cycles. The cycling stability of the cathode material obtained by changing the vacuum drying temperature is far inferior to that of the cathode material obtained by the embodiment 1 of the invention.
The examples of the invention and some of the electrical property data of the positive electrode material prepared in comparative examples are shown in the following table:
table 1 partial electrical property data comparison table
Figure BDA0002192997490000101
The data in the table show that the anode material obtained by the invention has higher specific discharge capacity and better cycling stability.
Reference documents:
[1]Kundu，D.；Adams，B.D.；Duffort，V.；Vajargah，S.H.；Nazar，L.F.A High-Capacity and Long-LifeAqueous Rechargeable Zinc Battery Using a Metal Oxide Intercalation Cathode.Nat. Energy 2016，1(10)，16119.
[2]He，P.；Zhang，G.；Liao，X.；Yan，M.；Xu，X.；An，Q.；Liu，J.；Mai，L.Sodium Ion Stabilized Vanadium Oxide Nanowire Cathodefor High-Performance Zinc-Ion Batteries.Adv.Energy Mater. 2018，8(10)，1702463.
[3]Xia，C.；Guo，J.；Li，P.；Zhang，X.；Alshareef，H.N.Highly Stable Aqueous Zinc-Ion Storage Using a Layered Calcium Vanadium Oxide Bronze Cathode.Angew.Chem.，Int.Ed.2018，57(15)， 3943-3948。

Claims (8)

1. a high-performance water-based zinc ion battery positive electrode material has the following general formula: (N, M)Σ＝1V8O20·nH2O, wherein N is one of Li, Na or K, M is one of Mn, Fe, Co or Ni, and N is 0.01-4;
the preparation method comprises the following steps:
weighing V2O5Fully dispersing the water-soluble salt of the metal N and the water-soluble salt of the metal M in water to obtain a mixed solution; adjusting the pH of the mixed solution to 1-4 by using an acetic acid aqueous solution; then carrying out hydrothermal reaction for 12-72h at the temperature of 90-200 ℃; centrifuging or filtering, washing and drying to obtain the anode material of the water-based zinc ion battery; the metal M is one of Mn, Fe, Co or Ni, and the metal N is one of Li, Na or K; weighing water-soluble salt and V of metal M according to the molar ratio of the metal M element, the vanadium element and the metal N element of 1-20:1-13:72O5And a water-soluble salt of metal N.
2. The high-performance aqueous zinc-ion battery positive electrode material according to claim 1, wherein the micro-morphology of the positive electrode material is a nanobelt, the length of the nanobelt is 0.2-1.5 μm, and the width of the nanobelt is 60-120 nm.
3. The high-performance aqueous zinc-ion battery positive electrode material according to claim 1, wherein the water-soluble salt of metal N is a sulfate, nitrate or chloride salt of metal N; the water-soluble salt of the metal M is a sulfate or nitrate of the metal M.
4. The method for producing a high-performance aqueous zinc-ion battery positive electrode material according to claim 1, characterized by comprising one or more of the following conditions:
a. in the mixed solution, V2O5The concentration of (A) is 0.1mol/L-0.7 mol/L;
b. the mass fraction of the acetic acid aqueous solution is 36-38%.
5. The high-performance aqueous zinc-ion battery positive electrode material as claimed in claim 1, wherein the hydrothermal reaction temperature is 120-190 ℃ and the reaction time is 24-72 h.
6. The high-performance aqueous zinc-ion battery positive electrode material according to claim 1, wherein the drying is vacuum drying at 40 to 90 ℃ for 8 to 20 hours.
7. Use of the high performance aqueous zinc-ion battery positive electrode material according to any one of claims 1 to 6 as a positive electrode material for a rechargeable aqueous zinc-ion battery.
8. The use of the high performance aqueous zinc-ion battery positive electrode material according to claim 7, in the preparation of a rechargeable aqueous zinc-ion battery, comprising the steps of:
(1) preparation of positive electrode plate
Uniformly mixing a positive electrode material, active carbon and polyvinylidene fluoride (PVDF) dissolved in N-methyl pyrrolidone to form slurry, coating the slurry on a titanium foil with the thickness of 20 mu m, wherein the coating thickness is 200-600 mu m, and drying to obtain a positive electrode plate; the mass ratio of the positive electrode material to the activated carbon to the polyvinylidene fluoride is 7:1.5: 1.5;
(2) preparation of negative electrode plate
The negative electrode is zinc foil with the thickness of 20-100 mu m, and the negative electrode slice is prepared by grinding, removing an oxidation layer, washing with ethanol and drying;
(3) preparation of the electrolyte
Dissolving zinc trifluoromethanesulfonate in deionized water to prepare electrolyte; the concentration of zinc trifluoromethanesulfonate in the electrolyte is 0.2-1.5 g/mL;
(4) preparation of the Battery
And placing the electrode plates into a battery case, placing a glass fiber diaphragm between the positive electrode plate and the negative electrode plate for separation, adding 50-80 mu L of electrolyte, and packaging the battery to obtain the rechargeable aqueous zinc ion battery.
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