CN113437368B - Method for improving capacity of anode material of water-based zinc ion battery based on static activation reaction - Google Patents
Method for improving capacity of anode material of water-based zinc ion battery based on static activation reaction Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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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
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Abstract
The invention provides a method for improving the capacity of a water system zinc ion battery anode material based on a static activation reaction, belonging to the field of chemistry; according to the invention, a vanadium-doped manganese dioxide material is synthesized by a hydrothermal method, then the vanadium-doped manganese dioxide material is mixed with a conductive agent and a binder to prepare a positive electrode, and is assembled with a zinc negative electrode and a zinc sulfate electrolyte to form a water-based zinc ion battery, and finally the assembled battery is stood at room temperature for a period of time, and high-activity pyro-vanadic acid zinc fibers are formed on the surface of the assembled battery, so that the purpose of improving the electrochemical activity and performance of an original electrode is achieved; the method has the advantages of simple operation, low cost, no pollution and wide application range.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a method for improving the capacity of a water system zinc ion battery anode material based on a static activation reaction.
Background
At present, the lithium ion battery is restricted by safety and cost and is difficult to meet the application requirement of large-scale energy storage in the energy storage market. Compared with a lithium ion battery, the water system zinc ion battery has the advantages of high safety performance, low cost, high energy density and the like, and is an ideal power supply of large-scale energy storage equipment. However, due to the strong electrostatic interaction between divalent zinc ions and positive active materials (such as manganese dioxide, etc.), zinc ions are difficult to intercalate and diffuse slowly, which seriously affects the electrochemical activity and zinc storage performance of manganese dioxide positive electrodes.
The electrochemical activation is a phenomenon that the electrode capacity gradually increases along with the increase of the cycle number, and can effectively improve the electrochemical activity of the manganese dioxide positive electrode, but the electrochemical activation is usually accompanied by the problems of complex crystal transformation, recrystallization, structural collapse and the like, so that the cycle performance of the battery is reduced, and the application of the electrochemical activation in the improvement of the electrochemical activity of the manganese dioxide positive electrode is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for improving the capacity of a water system zinc ion battery anode material based on a static activation reaction. According to the invention, vanadium-doped manganese dioxide serving as a positive electrode material of the water-based zinc ion battery is synthesized by a hydrothermal method, then the vanadium-doped manganese dioxide is mixed with a conductive agent and a binder to prepare a positive electrode, and the positive electrode, a zinc cathode and a zinc sulfate electrolyte are assembled to form the water-based zinc ion battery, and finally the assembled battery is placed at room temperature for a period of time, and high-activity zinc pyrovanadate fibers are formed on the surface of the battery, so that the purpose of improving the electrochemical activity and performance of an original electrode is achieved.
The invention provides a method for improving the capacity of a water system zinc ion battery anode material based on a static activation reaction, which specifically comprises the following steps:
adding manganese sulfate monohydrate and a sulfuric acid solution into deionized water, uniformly stirring, then adding a potassium permanganate solution and ammonium metavanadate solid, violently stirring and ultrasonically treating at room temperature to obtain a mixed solution, then carrying out hydrothermal reaction on the mixed solution, washing after the reaction is finished, and carrying out freeze drying to obtain a manganese dioxide material doped with vanadium of the cathode material of the water-based zinc ion battery;
mixing a vanadium-doped manganese dioxide material, a conductive agent, a binder and a solvent to prepare slurry, coating the slurry on the surface of a current collector, drying to obtain a positive electrode, assembling the positive electrode, an electrolyte and a zinc negative electrode to form a zinc ion battery, and finally performing static activation reaction on the assembled battery at room temperature to obtain the water-based zinc ion battery positive electrode material with improved electric capacity.
Further, the concentration of the sulfuric acid solution in the mixed solution is 0.5-0.6 mol/L, the concentration of the potassium permanganate solution in the mixed solution is 0.1-0.2 mol/L, and the pH range of the mixed solution is 1.5-2.5.
Further, the concentration of the manganese sulfate monohydrate in the mixed solution is 0.037mol/L, and the concentration of the ammonium metavanadate in the mixed solution is 0.03 mol/L.
Further, the hydrothermal reaction is carried out for 10-15 hours at the temperature of 100-150 ℃.
Further, the mole fraction of vanadium in the vanadium-doped manganese dioxide material is 5% -40%.
Further, the mass ratio of the vanadium-doped manganese dioxide material to the conductive agent to the binder is 6:2: 2-8: 1:1, and the amount of the solvent is only required to be mixed into slurry by the vanadium-doped manganese dioxide, the conductive agent and the binder.
Further, the conductive agent is one or more of acetylene black, ketjen black, SuperP, carbon fiber and carbon nano tube; the binder is one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE); the solvent is N-methylpyrrolidone (NMP); the current collector is one of titanium foil, stainless steel, carbon paper, carbon cloth and graphene paper.
Further, the drying condition is that the product is placed at the temperature of 60-120 ℃ for 6-48 hours.
Furthermore, the electrolyte can be one or more of zinc sulfate aqueous solution, zinc trifluoromethanesulfonate aqueous solution, zinc nitrate aqueous solution or other water-soluble zinc salts.
Further, the static activation is to place the mixture at room temperature for reaction for 1-90 days.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a static activation method of a cathode material of a water system zinc ion battery, which is characterized in that a vanadium-doped manganese dioxide material is synthesized by a hydrothermal method, a zinc sulfate aqueous solution is used as an electrolyte to assemble the water system zinc ion battery, and then the assembled battery is placed at room temperature for static activation reaction for a period of time, so that high-activity pyro-vanadic acid zinc fibers are spontaneously formed on the surface of the cathode, and the electrochemical activity and performance of the cathode material are improved. The method obviously improves the electrochemical activity of the manganese dioxide anode and effectively solves the problem of electrochemical activation.
The static activation method of the anode material of the water system zinc ion battery provided by the invention has no special requirements on the appearance, size, defect, valence state, preparation method and the like of the original electrode material, only needs the vanadium-doped anode material, and has lower production cost. And the method has simple activation procedure, is easy for industrialized popularization, can spontaneously perform static reaction to realize activation by placing the assembled battery for a period of time without other operations, has obvious activation effect, greatly improves the initial capacity, has higher capacity retention rate, and has the capacity retention rate of 99 percent after 100 cycles.
The method provided by the invention is simple to operate, low in cost and free of pollution, is not limited to the water-based zinc ion positive electrode material, and has certain applicability to other system battery positive and negative electrode materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of original positive electrode vanadium doped manganese dioxide.
FIG. 2 is an X-ray diffraction pattern of vanadium doped manganese dioxide/zinc pyrovanadate for activated anodes.
Fig. 3 is a comparison of the surface topography of the original anode and the activated anode, (a) is a scanning electron microscope photograph of the original anode; (b) scanning electron micrographs for activating the positive electrode. The inset is an optical photograph of the electrode surface.
FIG. 4 is a graph of Cyclic Voltammetry (CV) for an original positive electrode and an activated positive electrode, with a scan rate of 0.1 mV/s and a voltage range of 1.0-1.8V.
FIG. 5 is a graph of the cycling performance of the original anode and the activated anode, where the current density is 0.1A/g and the voltage range is 1.0-1.8V.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
adding 500mg of manganese sulfate monohydrate into 60mL of deionized water, stirring for 5min, adding 2mL of 0.5mol/L sulfuric acid solution, uniformly mixing, dropwise adding 20mL of 0.1mol/L potassium permanganate solution, adding 292 mg of ammonium metavanadate, stirring for 1h, and carrying out ultrasonic treatment for 0.5h to obtain a mixture. And then transferring the mixture into a hydrothermal reaction kettle, heating the mixture at the temperature of 120 ℃ for reaction for 12 hours, centrifugally washing the product for 6 times by using deionized water after the reaction is finished, and drying the product in a freeze dryer for 3 days.
FIG. 1 is an X-ray diffraction pattern of vanadium doped manganese dioxide as an original positive electrode, from which it can be seen that the product is ε -MnO 2 No diffraction peaks were found for vanadium oxide, indicating that vanadium is incorporated into the structure of manganese dioxide as a dopant ion.
Preparing a positive electrode by using vanadium-doped manganese dioxide as an active material, SuperP as a conductive agent, PVDF as a binder and NMP as a solvent, assembling the positive electrode, zinc sulfate electrolyte, a glass fiber diaphragm, a zinc negative electrode, a spring piece and a gasket into a button cell, and placing the assembled electrode at room temperature for 10 days.
And (3) disassembling the battery which is kept stand for 10 days, cleaning the surface of the positive electrode by using deionized water, and performing X-ray diffraction analysis after drying. Fig. 2 is an X-ray diffraction pattern of vanadium doped manganese dioxide/zinc pyrovanadate for activating the positive electrode, from which it can be seen that a diffraction peak of zinc pyrovanadate can be detected, indicating that a new active material is formed after activation.
Fig. 3 is a comparison of the surface topography of an original positive electrode and an activated positive electrode, wherein (a) is a scanning electron microscope photograph of the original positive electrode; (b) scanning electron micrographs for activating the positive electrode. The inset is an optical photograph of the electrode surface. As can be seen from the figure, the surface of the original positive electrode is found to be relatively flat, and white substances which can be seen by naked eyes are generated on the surface of the activated positive electrode, and scanning electron microscope pictures show that the white substances have fibrous appearances, fibers are hundreds of micrometers long, and are interwoven into a macroporous network structure.
CV tests are carried out on the original positive electrode and the activated positive electrode, FIG. 4 is a Cyclic Voltammetry (CV) graph of the original positive electrode and the activated positive electrode, wherein the scanning rate is 0.1 mV/s, the voltage range is 1.0-1.8V, and as can be seen from the graph, the area of a CV curve of the activated positive electrode is found to be remarkably increased, which shows that the capacity and the activity of the activated positive electrode are improved.
The original positive electrode and the activated positive electrode are subjected to cycle performance tests, fig. 5 is a cycle performance graph of the original positive electrode and the activated positive electrode, wherein the current density is 0.1A/g, the voltage range is 1.0-1.8V, and as can be seen from the graph, the capacity of the activated positive electrode is obviously higher than that of the original positive electrode, and the capacity retention rate is up to 99% after 100 cycles.
Example 2:
adding 500mg of manganese sulfate monohydrate into 70mL of deionized water, stirring for 8min, adding 2mL of 0.5mol/L sulfuric acid solution, uniformly mixing, dropwise adding 20mL of 0.1mol/L potassium permanganate solution, adding 245 mg of ammonium metavanadate, stirring for 1h, and carrying out ultrasonic treatment for 1h to obtain a mixture. And transferring the mixture into a hydrothermal reaction kettle, heating the mixture at the temperature of 100 ℃ for reaction for 15 hours, centrifugally washing the product for 5 times by using deionized water after the reaction is finished, and drying the product in a freeze dryer for 4 days.
The method comprises the steps of preparing a positive electrode by using vanadium-doped manganese dioxide as an active material, ketjen black as a conductive agent, PVDF as a binder and NMP as a solvent, assembling the positive electrode, zinc sulfate electrolyte, a glass fiber diaphragm, a zinc negative electrode, a spring piece and a gasket into a button cell, placing the assembled electrode at room temperature for 1 day, and enabling the shape, structure and performance of the activated positive electrode to be similar to those of example 1.
Example 3:
adding 500mg of manganese sulfate monohydrate into 50mL of deionized water, stirring for 10min, adding 2mL of 0.5mol/L sulfuric acid solution, uniformly mixing, dropwise adding 20mL of 0.1mol/L potassium permanganate solution, adding 196 mg of ammonium metavanadate, stirring for 2h, carrying out ultrasonic treatment on the mixture for 1h, transferring the mixture into a hydrothermal reaction kettle, and heating and reacting for 10h at the temperature of 150 ℃. And after the reaction is finished, centrifugally washing the product for 6 times by using deionized water, and drying the product for 5 days in a freeze dryer.
The method comprises the steps of preparing a positive electrode by using vanadium-doped manganese dioxide as an active material, a carbon nano tube as a conductive agent, PVDF as a binder and NMP as a solvent, assembling the positive electrode, zinc sulfate electrolyte, a glass fiber diaphragm, a zinc negative electrode, a spring piece and a gasket into a button cell, placing the assembled electrode at room temperature for 90 days, and enabling the shape, structure and performance of the activated positive electrode to be similar to those of example 1.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. A method for improving the capacity of a positive electrode material of a water system zinc ion battery based on a static activation reaction is characterized by comprising the following steps:
adding manganese sulfate monohydrate and a sulfuric acid solution into deionized water, uniformly stirring, then adding a potassium permanganate solution and an ammonium metavanadate solid, violently stirring and ultrasonically treating at room temperature to obtain a mixed solution, then carrying out hydrothermal reaction on the mixed solution, washing after the reaction is finished, and carrying out freeze drying to obtain a vanadium-doped manganese dioxide material of the anode material of the water-based zinc ion battery; the concentration of the sulfuric acid in the mixed solution is 0.5-0.6 mol/L, and the concentration of the potassium permanganate in the mixed solution is 0.1-0.2 mol/L; the concentration of the manganese sulfate monohydrate in the mixed solution is 0.037mol/L, and the concentration of the ammonium metavanadate in the mixed solution is 0.03 mol/L; the hydrothermal reaction is carried out under the condition of heating at 100-150 ℃ for 10-15 h;
mixing a vanadium-doped manganese dioxide material, a conductive agent, a binder and a solvent to prepare slurry, coating the slurry on the surface of a current collector, drying to obtain a positive electrode, assembling the positive electrode, an electrolyte and a zinc negative electrode to form a zinc ion battery, and finally performing static activation reaction on the assembled battery at room temperature to obtain the water-based zinc ion battery positive electrode material with improved electric capacity.
2. The method for improving the capacity of the positive electrode material of the water-based zinc-ion battery based on the static activation reaction according to claim 1, wherein the pH of the mixed solution is in a range of 1.5 to 2.5.
3. The method for improving the capacity of the anode material of the water-based zinc-ion battery based on the static activation reaction is characterized in that the mole fraction of vanadium in the vanadium-doped manganese dioxide material is 5% -40%.
4. The method for improving the capacity of the anode material of the water-based zinc-ion battery based on the static activation reaction is characterized in that the mass ratio of the vanadium-doped manganese dioxide material to the conductive agent to the binder is 6:2: 2-8: 1: 1.
5. The method for improving the capacity of the cathode material of the water-based zinc ion battery based on the static activation reaction is characterized in that the conductive agent is one or more of acetylene black, ketjen black, SuperP, carbon fiber and carbon nano tube; the binder is one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE); the solvent is N-methylpyrrolidone NMP; the current collector is one of titanium foil, stainless steel, carbon paper, carbon cloth and graphene paper.
6. The method for improving the capacity of the cathode material of the aqueous zinc-ion battery based on the static activation reaction according to claim 1, wherein when the cathode is obtained by drying, the drying is performed under the condition that the cathode is left at 60 to 120 ℃ for 6 to 48 hours.
7. The method for improving the capacity of the positive electrode material of the water-based zinc-ion battery based on the static activation reaction is characterized in that the electrolyte is one or more of zinc sulfate aqueous solution, zinc trifluoromethanesulfonate aqueous solution, zinc nitrate aqueous solution or other water-soluble zinc salts.
8. The method for improving the capacity of the positive electrode material of the water-based zinc-ion battery based on the static activation reaction according to claim 1, wherein the static activation is a standing reaction at room temperature for 1 to 90 days.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683757A (en) * | 2011-03-15 | 2012-09-19 | 清华大学深圳研究生院 | High-capacity rechargeable zinc ion battery |
| KR20180102505A (en) * | 2017-03-07 | 2018-09-17 | 세종대학교산학협력단 | Zn ion secondary battery having VO2(B) particles as electrode active material |
| CN110391415A (en) * | 2018-04-20 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials |
| CN110655114A (en) * | 2019-10-09 | 2020-01-07 | 东北大学 | Method for improving voltage of zinc ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683757A (en) * | 2011-03-15 | 2012-09-19 | 清华大学深圳研究生院 | High-capacity rechargeable zinc ion battery |
| KR20180102505A (en) * | 2017-03-07 | 2018-09-17 | 세종대학교산학협력단 | Zn ion secondary battery having VO2(B) particles as electrode active material |
| CN110391415A (en) * | 2018-04-20 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials |
| CN110655114A (en) * | 2019-10-09 | 2020-01-07 | 东北大学 | Method for improving voltage of zinc ion battery |
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