CN115799512A - Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth - Google Patents
Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth Download PDFInfo
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- CN115799512A CN115799512A CN202211516480.8A CN202211516480A CN115799512A CN 115799512 A CN115799512 A CN 115799512A CN 202211516480 A CN202211516480 A CN 202211516480A CN 115799512 A CN115799512 A CN 115799512A
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Abstract
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method and application of a cathode material of a water-based zinc ion battery capable of inhibiting dendritic crystal growth, which comprises the following steps: sequentially adding zinc nitrate and sodium selenite into deionized water, stirring, and adding hydrazine hydrate to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution, and washing, centrifuging and vacuum-drying the product to obtain ZnSe powder; adding ZnSe powder and polyvinylidene fluoride into an organic solvent, and stirring at room temperature to obtain zinc anode modified slurry; and coating the zinc anode modified slurry on a zinc foil, and performing vacuum drying to obtain the ZnSe @ Zn pole piece. According to the invention, the modified slurry is coated on the upper surface of the metal zinc electrode to form a protective coating with a certain thickness, the modified anode surface has the advantages of increasing the specific surface area, uniform electric field distribution and inducing zinc ions to be redistributed so as to realize homogenization, the coating effectively solves the problems of easy corrosion, dendritic crystal growth and the like of the zinc anode in the charging and discharging processes, and the electrochemical performance of the battery is obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method and application of a cathode material of a water-based zinc ion battery capable of inhibiting dendritic crystal growth.
Background
The development of clean energy sources such as wind energy and solar energy is severely limited due to large regional difference. Therefore, the development of an ideal large-scale energy storage system is urgently needed.
Since the development of commercialization, lithium ion batteries have been dominant in battery applications due to their high energy density and long cycle life. However, the lithium ion battery uses toxic and flammable organic electrolyte, so that great potential safety hazard exists, and people are in urgent need to find a substitute for the electrolyte. Aqueous Zinc Ion Batteries (ZIBs) proposed in recent years are attracting attention from researchers because of their advantages such as low cost, environmental friendliness, and high safety.
Zinc, as an amphoteric metal, is chemically active and can chemically react in both acidic and alkaline environments. Even in mild aqueous neutral electrolytes, problems of dendrite growth and "dead zinc" occur. The growth of zinc dendrites not only can puncture the separator causing cell shorting, but also negative electrode utilization and coulombic efficiency are low. In addition, because the adhesion between the dendrite and the metal is poor, the dendrite is easy to fall off from the surface of the zinc cathode to form dead zinc, and the battery capacity is reduced.
Therefore, in order to improve the reversibility of the battery, researchers have proposed many new methods to suppress dendrite growth, hydrogen evolution, corrosion, and the like, to obtain a more stable and efficient zinc negative electrode, including mainly methods of interface modification, structural design, electrolyte modification, and the like, but dendrite growth is still a problem that needs to be solved urgently by an aqueous zinc ion battery.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide preparation and application of a cathode material of a water-based zinc ion battery capable of inhibiting dendritic crystal growth.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
the invention provides a preparation method of a cathode material of a water-based zinc ion battery capable of inhibiting dendritic crystal growth, which comprises the following steps:
1) Adding zinc nitrate and sodium selenite into deionized water according to a molar ratio of 1; adding hydrazine hydrate according to the proportion of 4-20 ml of hydrazine hydrate/1 mol of zinc nitrate, and uniformly stirring again to obtain a mixed solution;
2) Adding the obtained mixed solution into a polytetrafluoroethylene lining, and then putting the polytetrafluoroethylene lining into a stainless steel high-pressure kettle for hydrothermal reaction;
3) Washing the precipitate obtained by the hydrothermal reaction with deionized water, centrifuging, and taking the precipitate again for vacuum drying to obtain ZnSe powder;
4) Adding ZnSe powder and polyvinylidene fluoride into an organic solvent according to the mass ratio of 8-10, and stirring at room temperature to obtain zinc anode modified slurry;
5) And coating the obtained zinc anode modified slurry on a zinc foil, and drying in vacuum to obtain the ZnSe @ Zn pole piece.
Further, in the preparation method of the cathode material of the water system zinc ion battery capable of inhibiting dendritic growth, in the step 1), the speed of two times of stirring is controlled to be 400-500 r/min.
Further, in the preparation method of the cathode material of the water system zinc ion battery capable of inhibiting dendritic crystal growth, in the step 2), the reaction temperature of the hydrothermal reaction is controlled to be 160-200 ℃, and the reaction time is controlled to be 20-25 h.
Further, in the preparation method of the cathode material of the water-based zinc ion battery capable of inhibiting dendritic crystal growth, in the step 3), the drying temperature of vacuum drying is controlled to be 60-80 ℃, and the drying time is controlled to be 10-15 h.
Further, in the preparation method of the cathode material of the water-based zinc ion battery capable of inhibiting dendritic crystal growth, in the step 4), the organic solvent is N-methylpyrrolidone; the stirring speed is controlled to be 300-450 r/min, and the stirring time is controlled to be 6-12 h.
Further, in the preparation method of the cathode material of the water system zinc ion battery capable of inhibiting dendritic crystal growth, in the step 5), the drying temperature of vacuum drying is controlled to be 60-100 ℃, and the drying time is controlled to be 6-12 h.
The invention also provides a battery cathode material which is prepared by the preparation method of the cathode material of the water-based zinc ion battery capable of inhibiting dendritic crystal growth.
The invention also provides an application of the battery cathode material in a water-based zinc ion battery. Assembling the ZnSe @ Zn pole piece as a negative electrode into a water system zinc ion battery, and testing the electrochemical performance of the water system zinc ion battery, wherein the test current density is 0.2-5mA/cm 2 The deposition capacity is 1mAh/cm 2 (ii) a The electrolyte used by the water-based zinc ion battery is 2mol/L ZnSO 4 Solution or 3mol/L ZnSO 4 And (3) solution.
The invention has the beneficial effects that:
1. according to the invention, coating modification is carried out on the surface of the metal zinc anode, and due to the unique nano-particle structure of ZnSe, the modified surface can be uniformly distributed by an electric field, so that zinc ions are induced to be uniformly nucleated and deposited again, the polarization and the growth of dendritic crystals are reduced, and the cycle performance of the battery is improved.
2. The invention adopts a one-step hydrothermal method, can greatly simplify the preparation method and has simple process.
3. According to the invention, the coating modification is carried out on the surface of the metal zinc anode, and the modified zinc cathode is uniformly electroplated and stripped below the coating, so that the growth of dendrites is inhibited, the short circuit caused by the penetration of a diaphragm is avoided, and the coulomb efficiency and the cycle performance of the battery are improved.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM photograph of ZnSe @ Zn electrode in example 1;
FIG. 2 is a chronoamperometric graph of symmetric cells assembled with zinc electrode tabs in example 1 and comparative example 1 at-150 mV overpotential;
FIG. 3 shows the current density of 1mA/cm for the symmetrical batteries assembled with the zinc electrode sheets in example 1 and comparative example 1 2 And a deposition capacity of 1mAh/cm 2 Lower strip/plate cycle profile;
wherein, a-example 1, b-comparative example 1;
FIG. 4 shows the current density of 0.2-5mA/cm for the symmetrical batteries assembled with the zinc electrode sheets in example 1 and comparative example 1 2 The deposition capacity is 1mAh/cm 2 A lower magnification cycle chart;
wherein, a-example 1, b-comparative example 1;
fig. 5 is an EIS graph of symmetric batteries assembled with zinc electrode tabs in example 1 and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the invention, the modified slurry is coated on the upper surface of the metal zinc electrode to form a protective coating with a certain thickness, the modified anode surface is increased in specific surface area, the electric field distribution is uniform, and zinc ions are induced to be redistributed to realize homogenization.
The specific embodiment of the invention is as follows:
example 1
1) Preparation of zinc cathode material
0.595g of zinc nitrate and 0.692g of sodium selenite are weighed and dispersed in 30mL of water, stirred on a magnetic stirrer for 20 minutes, 5mL of hydrazine hydrate is weighed and dropped into the solution, the solution is stirred for 30 minutes, then the solution is put into a reaction kettle, and the hydrothermal temperature is 180 ℃ for 24 hours. After the reaction is finished, centrifugally washing the reactant for three times by using deionized water, collecting the washed product, and placing the product in a drying box for vacuum drying for 12 hours at the temperature of 60 ℃ to obtain ZnSe powder.
And (2) uniformly mixing the prepared ZnSe powder and polyvinylidene fluoride according to the weight ratio of 9.
Uniformly coating the zinc anode modified slurry on the treated zinc foil by using a tetrahedral film coater, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a ZnSe modified zinc cathode material-ZnSe @ Zn electrode, wherein the SEM result is shown in figure 1; wherein the thickness of the coating is 15 μm.
2) Assembling symmetrical batteries
The prepared zinc negative electrode material is cut into electrode slices with the diameter of 12mm by a slicing machine, and two same electrode slices are used as a positive electrode slice and a negative electrode slice. Putting a zinc negative pole piece into a positive shell, ensuring that one surface with a coating is in contact with the diaphragm, then putting the glass fiber diaphragm, dripping 300uL2mol/L zinc sulfate serving as electrolyte into the glass fiber diaphragm by using a liquid transfer gun, and then putting another zinc negative pole piece above the diaphragm. And (3) similarly, contacting one surface with the coating with a diaphragm, sequentially putting a gasket and a spring plate, finally buckling the negative electrode shell, and packaging the battery by using a battery packaging machine to obtain the modified zinc negative electrode water system zinc ion symmetrical button battery marked as ZnSe @ Zn// ZnSe @ Zn symmetrical button battery.
Example 2
This example is substantially the same as example 1 except that the thickness of the coating layer is 10 μm.
Example 3
This example is substantially the same as example 1 except that the thickness of the coating layer is 20 μm.
Comparative example 1
1) Preparation of zinc cathode material
Firstly, preprocessing a zinc sheet: preparing 0.01mol/L dilute hydrochloric acid, putting the zinc foil into the dilute hydrochloric acid, performing ultrasonic treatment for 1 to 3 minutes, washing with deionized water for 3 to 5 times to remove the residual dilute hydrochloric acid, and finally performing ultrasonic treatment for 1 to 3 minutes with ethanol. And naturally drying the treated zinc foil at room temperature for later use. The purpose is to remove the oxide layer generated in the air and the surface impurities of the zinc foil. And the pretreated zinc sheet is used as a zinc cathode material.
2) Assembling symmetrical batteries
The prepared zinc negative electrode material is cut into electrode slices with the diameter of 12mm by a slicing machine, and two same electrode slices are used as a positive electrode slice and a negative electrode slice. Putting a zinc negative pole piece into a positive shell, ensuring that one surface with a coating is in contact with a diaphragm, then putting a glass fiber diaphragm, dropping 300uL2mol/L zinc sulfate as electrolyte, and then putting another zinc negative pole piece above the diaphragm. And (3) similarly, contacting one surface with the coating with a diaphragm, then sequentially placing a gasket and a spring plate, finally buckling a negative electrode shell, and packaging the battery by using a battery packaging machine to obtain the modified zinc negative electrode water system zinc ion symmetrical button battery, wherein the label is Zn// Zn symmetrical button battery.
Under the same test conditions, the polarization voltage and the cycling stability of the coatings with different thicknesses are different. The invention was tested to achieve the minimum poling voltage and the longest cycle time at a coating thickness of 15 μm.
The cathodes of the examples 1-3 and the comparative example 1 are assembled into a symmetrical battery to be subjected to cycle performance test, an artificial interface is constructed on the surface of the zinc anode to modify the zinc anode, and the prepared protective layer has very small polarization voltage in the battery cycle process (the<30 mV) at a current density of1mA/cm 2 The deposition capacity is 1mAh/cm 2 The cycle can be carried out for 650 hours, and the polarization voltage is almost kept unchanged; the unmodified zinc cathode can only be cycled for 60 hours, and the modified coating shows the stability and long cycle life.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A preparation method of a cathode material of an aqueous zinc ion battery capable of inhibiting dendritic crystal growth is characterized by comprising the following steps:
1) Adding zinc nitrate and sodium selenite into deionized water according to a molar ratio of 1; adding hydrazine hydrate according to the proportion of 4-20 ml of hydrazine hydrate/1 mol of zinc nitrate, and uniformly stirring again to obtain a mixed solution;
2) Adding the obtained mixed solution into a polytetrafluoroethylene lining, and then putting the polytetrafluoroethylene lining into a stainless steel autoclave for hydrothermal reaction;
3) Washing the precipitate obtained by the hydrothermal reaction with deionized water, centrifuging, and taking the precipitate again for vacuum drying to obtain ZnSe powder;
4) Adding ZnSe powder and polyvinylidene fluoride into an organic solvent according to the mass ratio of 8-10, and stirring at room temperature to obtain zinc anode modified slurry;
5) And coating the obtained zinc anode modified slurry on a zinc foil, and performing vacuum drying to obtain the ZnSe @ Zn pole piece.
2. The method for producing an aqueous zinc-ion battery negative electrode material that can suppress dendrite growth according to claim 1, characterized in that: in the step 1), the speed of the two-time stirring is controlled to be 400-500 r/min.
3. The method for producing an aqueous zinc-ion battery negative electrode material that can suppress dendrite growth according to claim 1, characterized in that: in the step 2), the reaction temperature of the hydrothermal reaction is controlled to be 160-200 ℃, and the reaction time is controlled to be 20-25 h.
4. The method for preparing an aqueous zinc ion battery anode material capable of suppressing dendrite growth according to claim 1, wherein the method comprises the steps of: in the step 3), the drying temperature of vacuum drying is controlled to be 60-80 ℃, and the drying time is controlled to be 10-15 h.
5. The method for producing an aqueous zinc-ion battery negative electrode material that can suppress dendrite growth according to claim 1, characterized in that: in the step 4), the organic solvent is N-methyl pyrrolidone; the stirring speed is controlled to be 300-450 r/min, and the stirring time is controlled to be 6-12 h.
6. The method for producing an aqueous zinc-ion battery negative electrode material that can suppress dendrite growth according to claim 1, characterized in that: in the step 5), the drying temperature of vacuum drying is controlled to be 60-100 ℃, and the drying time is controlled to be 6-12 h.
7. A battery negative electrode material prepared by the method for preparing the aqueous zinc ion battery negative electrode material capable of inhibiting dendritic crystal growth according to any one of claims 1 to 6.
8. Use of the battery anode material according to claim 7 in an aqueous zinc ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116314579A (en) * | 2023-05-22 | 2023-06-23 | 西北工业大学 | Preparation method of multifunctional interface layer modified zinc anode |
| CN117199229A (en) * | 2023-10-27 | 2023-12-08 | 中南大学 | Preparation method and application of zinc blende-based multifunctional interface layer modified composite zinc anode |
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2022
- 2022-11-29 CN CN202211516480.8A patent/CN115799512A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116314579A (en) * | 2023-05-22 | 2023-06-23 | 西北工业大学 | Preparation method of multifunctional interface layer modified zinc anode |
| CN116314579B (en) * | 2023-05-22 | 2023-08-08 | 西北工业大学 | Preparation method of multifunctional interface layer modified zinc anode |
| CN117199229A (en) * | 2023-10-27 | 2023-12-08 | 中南大学 | Preparation method and application of zinc blende-based multifunctional interface layer modified composite zinc anode |
| CN117199229B (en) * | 2023-10-27 | 2024-03-19 | 中南大学 | Preparation method and application of zinc blende-based multifunctional interface layer modified composite zinc anode |
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