CN117577766A - Preparation method of zinc negative electrode protective coating for water-based zinc ion battery - Google Patents
Preparation method of zinc negative electrode protective coating for water-based zinc ion battery Download PDFInfo
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- CN117577766A CN117577766A CN202311420117.0A CN202311420117A CN117577766A CN 117577766 A CN117577766 A CN 117577766A CN 202311420117 A CN202311420117 A CN 202311420117A CN 117577766 A CN117577766 A CN 117577766A
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- 239000011701 zinc Substances 0.000 title claims abstract description 79
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 65
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011253 protective coating Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 10
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 4
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000002345 surface coating layer Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 229920000767 polyaniline Polymers 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a preparation method of a zinc negative electrode protective coating for a water-based zinc ion battery, which takes a metal zinc negative electrode as a substrate, and utilizes sulfonated polyaniline and acrylic resin to be uniformly mixed in ethanol to prepare the protective coating with conductive and anti-corrosion functions. The invention can well inhibit the dendrite growth and corrosion reaction of the zinc cathode, and endows the water-based zinc ion battery with better cycle life and higher cycle stability.
Description
Technical Field
The invention belongs to the technical field of novel battery electrode material functional coatings, and particularly relates to a preparation method of a zinc negative electrode protective coating for a water-based zinc ion battery.
Background
Along with the rapid development of science and technology and industrialization, the sustainable and environment-friendly novel energy demand is gradually increased, and meanwhile, the application and research of efficient and simple electrochemical energy storage equipment are also gradually increased. At present, related researches on water-based zinc ion batteries are vigorously developed, and water-based electrolyte is adopted, so that the water-based zinc ion battery is more environment-friendly and safer. In addition, the metal zinc cathode has the advantages of high theoretical specific capacity (820 mAh/g), lower oxidation-reduction potential (-0.762V, relative to a standard hydrogen electrode) and the like, and becomes one of the focus attention in the field of novel secondary batteries at present, and is considered to be an electrochemical energy storage device with the most development potential in the future.
However, similar to the metallic lithium negative electrode, the metallic zinc negative electrode inevitably encounters problems of dendrite, hydrogen evolution, corrosion and the like in the aqueous electrolyte, which affects the deposition dissolution efficiency and stability of the metallic zinc negative electrode, thereby causing the overall performance of the aqueous zinc battery system to be reduced. At present, reversibility and stability of a metal zinc negative electrode can be obviously improved through interface modification of the zinc negative electrode, three-dimensional electrode structure design and electrolyte optimization strategies, and then construction of a conductive and corrosion-resistant functional coating of the zinc negative electrode is seldom concerned. It is generally believed that the conductive functional coating with smaller diffusion channels can protect the metal substrate and enhance its corrosion protection properties by blocking molecular diffusion effects. Moreover, the sulfonic acid group and the carbon nitrogen group can be used as active adsorption sites and can also redistribute a zinc ion concentration field, and uniform and reversible deposition of zinc ions in the water-based electrolyte is further realized by adjusting the zinc deposition dissolution rate.
Disclosure of Invention
The technical problems to be solved are as follows:
aiming at the defects of the existing water system zinc ion electrode material technology, the application solves the technical problems of dendrite growth, hydrogen evolution, corrosion and the like of the original zinc cathode, and provides a preparation method of a zinc cathode protective coating for a water system zinc ion battery; the preparation process is simple, green and environment-friendly; the problems of dendrite growth, hydrogen evolution, corrosion and the like in the water-based zinc ion battery can be well inhibited, so that the stability and reversibility of the metal zinc cathode in the water-based electrolyte are improved.
The technical scheme is as follows:
in order to achieve the above purpose, the present application is implemented by the following technical schemes:
the preparation method of the zinc cathode protective coating for the water-based zinc ion battery is obtained by uniformly mixing sulfonated polyaniline SPANI and water-based resin in ethanol, and specifically comprises the following steps:
the first step: mixing and stirring 1 part of aniline ANI and 0.1-5 parts of o-aminobenzenesulfonic acid in hydrochloric acid for 1 hour at room temperature according to the weight part ratio to obtain a solution A; dissolving 0.2-5 parts of ammonium persulfate APS in hydrochloric acid at room temperature to obtain solution B;
and a second step of: stirring and mixing the solution A and the solution B at the speed of 400r/min, standing at room temperature for 24 hours, centrifugally separating the solution, washing the solution with deionized water until the pH value of supernatant is 5-6, filtering out precipitate to obtain SPANI, and finally drying the obtained solid in vacuum;
respectively weighing 1-100 parts of water-based resin, 50-1000 parts of ethanol and 1 part of the SPANI prepared in the second step according to the mass part ratio, firstly mixing acrylic resin with ethanol, then performing ultrasonic dispersion, then adding the SPANI into the system, continuing ultrasonic dispersion to obtain zinc anode protective coating paint, and uniformly coating the paint on zinc sheets;
fourth step: and (3) naturally airing the zinc sheet coated in the third step to obtain the metal zinc anode with the surface coating layer.
Further, in the first step reagent A and the reagent B, the hydrochloric acid is 0.1mol/L-2mol/L, and the dosage is 40mL.
Further, the second step of centrifugation speed is 3000-10000rpm, the centrifugation time is less than or equal to 40min, the drying temperature is 40-100 ℃, and the drying time is 12-24h.
Further, the water-based resin in the third step is one or more of acrylic resin, epoxy resin and polyurethane, and the concentration of the ethanol is 75-100%.
Further, according to the mass portion ratio, SPANI: acrylic resin: ethanol=1: 50:1000.
further, in the third step, the zinc sheet is zinc foil, and the thickness of the coating layer is controlled to be 5-100 mu m.
And further, the fourth step of naturally airing is carried out for 24-48 hours at room temperature, and the metallic zinc anode protected by the coating is obtained.
Further, the coating mode is one or more of spin coating, knife coating and spray coating.
Further, the thickness of the zinc sheet is 0.05mm-0.1mm, and the purity is more than 95%.
The technical principle of the application is as follows: the sulfonated polyaniline with good conductivity and barrier effect is adopted as a coating material, so that the sulfonated polyaniline is adsorbed and bonded on the surface of the metal zinc negative electrode to protect the zinc negative electrode from corrosion, and meanwhile, the high electrical property of the conductive polymer can promote the transmission of zinc ions.
The beneficial effects are that:
the application provides a preparation method of a zinc cathode protective coating for a water-based zinc ion battery, which has the following beneficial effects compared with the prior art:
1. aiming at the problems of dendrite, hydrogen evolution, corrosion and the like of a zinc cathode in the cyclic use process of the current water-based zinc ion battery, the application provides an electrode protective coating prepared by taking acrylic resin as a base and matching with SPANI (sulfonated polyaniline) as a coating, so that the diffusion kinetics of zinc ions can be accelerated, the growth of dendrite is inhibited, and meanwhile, a stable interface layer can be formed, so that the interface transmission of the zinc ions is stabilized;
2. the zinc cathode coating paint applied to the water-based zinc ion battery is environment-friendly, and the material preparation method is simple;
3. the application provides a coating material based on the research on the mechanism of improving the surface of a metal electrode, when the coating material is coated on the surface of a zinc anode, the zinc anode is endowed with higher hydrogen evolution overpotential and stronger corrosion resistance to a certain extent, the reversibility and the circulation stability of a new metal anode are improved, and the coating material has better application prospect in the field of water-based zinc secondary batteries;
4. the metallic zinc cathode protected by the coating has the current density of 5mA cm -2 The dough kneading capacity is 5mAh cm -2 The assembled symmetrical cell was also able to be cycled stably for 250 hours.
Drawings
FIG. 1 is a graph showing that the protective coating provided by the present application was applied as a metallic zinc anode functional coating at a current density of 0.5mA cm -2 The surface capacity was 0.5mAh cm -2 The charge-discharge curve diagram of the symmetric battery of the water system zinc ion battery;
FIG. 2 is a graph showing that the protective coating provided in the present application was applied as a metallic zinc anode functional coating at a current density of 5mA cm -2 The surface capacity was 5mAh cm -2 The charge-discharge curve graph of the asymmetric battery;
FIG. 3 is a graph showing that the protective coating provided by the present application was applied as a metallic zinc anode functional coating at a current density of 0.5mA cm -2 The surface capacity was 0.5mAh cm -2 And (3) a coulombic efficiency diagram of the SPANI-Cu// Zn asymmetric battery.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present invention, and equivalent changes and modifications are also within the scope of the present application as defined in the claims.
Example 1:
the preparation method of the zinc cathode protective coating for the water-based zinc ion battery is obtained by uniformly mixing sulfonated polyaniline SPANI and water-based resin in ethanol, and specifically comprises the following steps:
the first step: mixing and stirring 0.728mL of aniline ANI and 1.38g of o-aminobenzenesulfonic acid in 0.1mol/L and 40mL of hydrochloric acid at room temperature for 1 hour to obtain a reagent A; 3.648g of ammonium persulfate APS is measured at room temperature and dissolved in 0.1mol/L and 40mL of hydrochloric acid, and the mixture is mixed and stirred for 1 hour to obtain a reagent B;
and a second step of: rapidly mixing A, B reagent, standing at room temperature for 24 hr, centrifuging the solution at 5000rpm for 30min; washing with deionized water until the pH value of the supernatant is 5, filtering out precipitate to obtain SPANI, and finally drying the obtained solid in vacuum;
thirdly, weighing 1mg of SPANI, 50mg of acrylic resin and 1000mg of ethanol with concentration of 80%, firstly mixing the acrylic resin with the ethanol, performing ultrasonic dispersion, and then adding the SPANI into the system to perform ultrasonic dispersion continuously to obtain the zinc anode protective coating paint of the example 2:
application of zinc cathode protective coating in water-based zinc ion battery
The zinc foil used in this example had a thickness of 0.1mm and a diameter of 12mm.
The first step: preparation of negative electrode plate
The zinc negative electrode protective coating prepared in example 1 was uniformly coated on a zinc foil wafer by a knife coating method, the coating thickness was 25 μm, and dried at room temperature for 24 hours, to obtain a metallic zinc negative electrode.
The zinc negative electrode protective coating prepared in example 1 was uniformly coated on a copper foil wafer by a knife coating method, the coating thickness was 25 μm, and the copper negative electrode sheet was obtained by drying at room temperature for 24 hours.
And a second step of: assembly of symmetrical batteries
The assembly method comprises the following steps: the pure zinc foil is used as a positive electrode plate of the button cell, and the metallic zinc negative electrode prepared in the first step is used as a negative electrode plate of the button cell. Placing two titanium meshes into a shell, firstly placing a negative electrode plate, ensuring that one surface with a coating contacts a diaphragm, then placing a glass fiber diaphragm, and dripping ZnSO 4 And (3) placing an anode zinc sheet above the diaphragm, buckling the other half of the shell, and packaging the battery by using a battery packaging machine to obtain the symmetrical button battery consisting of the anode pole piece with the protective coating and the anode zinc sheet, wherein the symmetrical button battery is marked as SPANI-Zn// Zn symmetrical button battery.
Comparative example 1
Aqueous zinc ion symmetric button cell of pure zinc electrode: the assembly method was the same as in example 2 except that 99% pure zinc foil was used for both the positive and negative plates, labeled Zn// Zn symmetrical coin cell.
The Zn// Zn symmetrical button cell assembled by the SPANI-Zn functional coating is 0.5mAcm -2 The dough kneading capacity is 0.5mAh cm -2 The performance of the lower voltage-time curve is shown in figure 1. The results show that SPANI-Zn// Zn can withstand 1500 hoursStable circulation and no short circuit phenomenon, which is better than the bare zinc sheet in ZnSO reported in the previous study 4 Electrochemical performance in an electrolyte.
Assembly of asymmetric battery
The assembly method comprises the following steps: the pure zinc foil is used as the positive electrode plate of the button cell, and the copper negative electrode plate prepared in the first step in the example 2 is used as the negative electrode plate of the button cell. Placing two titanium meshes into a shell, placing zinc sheets again to ensure that one surface with a coating contacts a diaphragm, then placing a glass fiber diaphragm, and dripping ZnSO 4 And (3) placing an electrolyte above the diaphragm, then placing a positive electrode plate above the diaphragm, fastening the other half of the casing, and packaging the battery by a battery packaging machine to obtain the asymmetric button battery consisting of the copper negative electrode plate and the positive electrode plate with the protective coating, wherein the asymmetric button battery is marked as SPANI-Cu// Zn asymmetric button battery. The coulombic efficiency of the SPANI-Cu// Zn and the charge-discharge curves thereof are shown in figures 2 and 3, and the result shows that the average coulombic efficiency of the SPANI-Cu// Zn is about 99% after 150 cycles of charge-discharge.
Comparative example 2
Aqueous zinc ion asymmetric button cell of pure zinc copper electrode: the assembly method is the same as that of comparative example 1, except that the positive electrode plate uses zinc foil, the negative electrode plate uses pure copper foil, and the Cu// Zn asymmetric button cell is marked.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and that the general principles described herein may be applied to other embodiments without the need for inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. A preparation method of a zinc cathode protective coating for a water-based zinc ion battery is characterized by comprising the following steps of
Is obtained by evenly mixing the water-based resin with ethanol, and specifically comprises the following steps:
the first step: mixing and stirring 1 part of aniline ANI and 0.1-5 parts of o-aminobenzenesulfonic acid in hydrochloric acid for 1 hour at room temperature according to the weight part ratio to obtain a solution A; dissolving 0.2-5 parts of ammonium persulfate APS in hydrochloric acid at room temperature to obtain solution B;
and a second step of: stirring and mixing the solution A and the solution B at the speed of 400r/min, standing at room temperature for 24 hours, centrifugally separating the solution, washing the solution with deionized water until the pH value of supernatant is 5-6, filtering out precipitate to obtain SPANI, and finally drying the obtained solid in vacuum;
respectively weighing 1-100 parts of water-based resin, 50-1000 parts of ethanol and 1 part of the SPANI prepared in the second step according to the mass part ratio, firstly mixing acrylic resin with ethanol, then performing ultrasonic dispersion, then adding the SPANI into the system, continuing ultrasonic dispersion to obtain zinc anode protective coating paint, and uniformly coating the paint on zinc sheets;
fourth step: and (3) naturally airing the zinc sheet coated in the third step to obtain the metal zinc anode with the surface coating layer.
2. The method for preparing a zinc cathode protective coating for an aqueous zinc ion battery according to claim 1, wherein the hydrochloric acid in the first step reagent A and the reagent B is 0.1mol/L-2mol/L, and the dosage is 40mL.
3. The method for preparing a zinc anode protective coating for a water-based zinc ion battery according to claim 1, wherein the second step is performed at a centrifugation speed of 3000-10000rpm for less than or equal to 40min, the drying temperature is 40-100 ℃, and the drying time is 12-24h.
4. The method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 1, characterized in that: the water-based resin in the third step is one or more of acrylic resin, epoxy resin and polyurethane, and the concentration of the ethanol is 75-100%.
5. The method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 4, wherein: according to the mass portion ratio, SPANI: acrylic resin: ethanol=1: 50:1000.
6. the method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 1, characterized in that: in the third step, the zinc sheet is zinc foil, and the thickness of the coating layer is controlled to be 5-100 mu m.
7. The method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 1, characterized in that: and step four, naturally airing for 24-48 hours at room temperature to obtain the metal zinc cathode protected by the coating.
8. The method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 6, wherein: the coating mode is one or more of spin coating, knife coating and spray coating.
9. The method for preparing a zinc anode protective coating for an aqueous zinc ion battery according to claim 1, characterized in that: the thickness of the zinc sheet is 0.05mm-0.1mm, and the purity is more than 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311420117.0A CN117577766A (en) | 2023-10-30 | 2023-10-30 | Preparation method of zinc negative electrode protective coating for water-based zinc ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311420117.0A CN117577766A (en) | 2023-10-30 | 2023-10-30 | Preparation method of zinc negative electrode protective coating for water-based zinc ion battery |
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| Publication Number | Publication Date |
|---|---|
| CN117577766A true CN117577766A (en) | 2024-02-20 |
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|---|---|---|---|
| CN202311420117.0A Pending CN117577766A (en) | 2023-10-30 | 2023-10-30 | Preparation method of zinc negative electrode protective coating for water-based zinc ion battery |
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| Country | Link |
|---|---|
| CN (1) | CN117577766A (en) |
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- 2023-10-30 CN CN202311420117.0A patent/CN117577766A/en active Pending
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