CN117317122A - Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof - Google Patents
Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117317122A CN117317122A CN202311520686.2A CN202311520686A CN117317122A CN 117317122 A CN117317122 A CN 117317122A CN 202311520686 A CN202311520686 A CN 202311520686A CN 117317122 A CN117317122 A CN 117317122A
- Authority
- CN
- China
- Prior art keywords
- zinc
- stirring
- time
- room temperature
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011701 zinc Substances 0.000 title claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000002033 PVDF binder Substances 0.000 claims abstract description 5
- 229910007565 Zn—Cu Inorganic materials 0.000 claims abstract description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention belongs to the technical field of energy materials, and in particular relates to a zinc anode material with high specific surface area and zinc affinity, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Preparing a mixed solution; 2) Aging the prepared mixed solution at room temperature to generate a precipitate; 3) Washing the obtained precipitate with methanol, centrifuging, and vacuum drying to obtain blue powder; 4) Placing blue powder into a porcelain boat, and calcining to obtain Cu@C; 5) Adding Cu@C and polyvinylidene fluoride white powder into an organic solvent, and stirring to obtain slurry; 6) And coating the slurry on zinc foil, and vacuum drying to obtain the Zn-Cu@C pole piece. The invention is to modify a layer of coating material with high specific surface area and zinc affinity on the surface of the zinc cathode, the modified interface can enhance the diffusion kinetics of zinc ions and reduce the nucleation overpotential of zinc, promote the uniform deposition of zinc ions, inhibit the growth of dendrites and reduce the occurrence of polarization and side reaction, thereby improving the cycle performance of the battery.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a zinc anode material with high specific surface area and zinc affinity, and a preparation method and application thereof.
Background
The ever-increasing energy demand and increasingly depleted fossil energy have forced people to find alternative energy sources. In the past decades, although clean energy sources such as wind energy, water energy and solar energy have been widely developed, these energy sources cannot be used on a large scale because they are greatly affected by regions. In order to meet the continuous supply of clean energy in the future and the daily needs of people, lithium ion batteries have become the first choice in energy storage systems. However, due to shortage of lithium ore resources, the price is continuously increased, and the flammability and toxicity of the organic electrolyte have great potential safety hazards and environmental protection problems, which are important factors for limiting the further development of the lithium ion battery.
The water-based zinc ion battery is considered as the most promising substitute in the lithium ion battery because of the characteristics of abundant reserves, convenient assembly and the like. And the neutral electrolyte in the water-based zinc ion battery is environment-friendly, has higher ionic conductivity and can provide more energy output.
However, dendrites are very easily grown on the surface of the negative electrode during charge and discharge cycles of the battery due to non-uniform deposition and stripping of metallic zinc, and the dendrite formation not only results in low coulombic efficiency, but also pierces the separator in severe cases, causing short circuit of the battery. In addition, dendrites consume a large amount of active material, resulting in a decrease in the capacity of the anode. On the other hand, metallic zinc and H + Generating hydrogen evolution reaction to generateThe hydrogen gas of (2) increases the pressure inside the cell, causing the cell to expand; OH (OH) - Byproducts generated by the reaction with metallic zinc can cover the active sites on the zinc surface. These problems seriously impair the cycle life of the battery.
Therefore, in order to improve the reversibility and electrochemical performance of the battery, researchers have proposed many new methods to inhibit dendrite growth, hydrogen evolution, corrosion and other problems, so as to obtain a more stable and efficient zinc anode, wherein the methods mainly comprise surface modification, structural design, alloy strategies and the like. However, dendrite growth remains a critical issue to be addressed by aqueous zinc ion batteries.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a zinc anode material with high specific surface area and zinc affinity, a preparation method and application thereof, and the surface of zinc metal is coated with a protective layer by means of surface modification, so that the direct contact between water and zinc metal can be physically isolated, nucleation overpotential can be reduced, and Zn can be realized 2+ Thereby achieving the purposes of inhibiting dendrite growth and improving the cycle performance of the battery.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the invention provides a preparation method of a zinc anode material with high specific surface area and zinc affinity, which comprises the following steps:
1) Adding copper nitrate and polyvinylpyrrolidone into a methanol solution, dissolving terephthalic acid into the methanol solution, stirring at room temperature for a period of time, adding a copper nitrate and polyvinylpyrrolidone mixed solution into the terephthalic acid solution, and stirring at room temperature to obtain a mixed solution;
2) Aging the prepared mixed solution at room temperature to generate a precipitate;
3) Washing the obtained precipitate with methanol, centrifuging, and vacuum drying to obtain blue powder;
4) Placing blue powder into a porcelain boat, heating to 400-700 ℃ in a tube furnace at a certain heating rate under argon atmosphere, preserving heat for a period of time, and naturally cooling to room temperature to obtain an intermediate product Cu@C;
5) Adding an intermediate product Cu@C and polyvinylidene fluoride white powder into an organic solvent according to the mass ratio of 8-10:1, and stirring at room temperature to obtain zinc metal negative electrode modification layer slurry;
6) And coating the zinc metal negative electrode modification layer slurry on zinc foil, and vacuum drying to obtain the Zn-Cu@C pole piece.
Further, in the step 1), the mass ratio of copper nitrate, polyvinylpyrrolidone and terephthalic acid is as follows: 0.5 to 1: 0.2-0.6:0.3-0.7.
Further, in the step 1), the stirring speed is 300-500 r/min, and the stirring time is 5-15 min.
Further, in the step 2), the aging time is 12-24 hours.
Further, in the step 3), the vacuum drying temperature is 60-80 ℃ and the drying time is 8-12 h.
Further, in the step 4), the temperature rising rate is 1-5 ℃/min, and the heat preservation time is 2-5 h.
Further, in the step 5), the organic solvent is N-methyl pyrrolidone, and the stirring time is 6-8 hours.
Further, in the step 6), the vacuum drying temperature is 60-80 ℃ and the drying time is 6-12 h, and the coating mode is a knife coating method.
The invention also provides a zinc anode material with high specific surface area and zinc affinity, which is prepared by the preparation method.
The invention also provides application of the zinc anode material in preparing a water system zinc ion battery anode. The electrolyte used in the water-based zinc ion battery is 2mol/LZnSO 4 Solution or 3mol/LZnSO 4 A solution.
The beneficial effects of the invention are as follows:
1. according to the invention, a layer of coating material with high specific surface area and zinc affinity is modified on the surface of the zinc anode, the modified interface can increase the diffusion kinetics of ions, the direct contact between the anode and water is physically isolated, and the occurrence of hydrogen evolution reaction and side reaction is reduced.
2. The invention has simple operation, and the coating method can accurately control the thickness of the coating.
3. The zinc-philicity of copper particles can reduce polarization and zinc nucleation energy barrier, promote Zn 2+ And (5) uniformly nucleating.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a Cu@C material;
FIG. 2 is a long cycle graph of the zinc electrode tab assembled symmetrical cell of examples 1-3;
FIG. 3 is a graph of the magnification of a symmetric cell assembled from zinc electrode tabs in examples 1-3;
FIG. 4 is a graph of nucleation overpotential for Zn// Cu half cells assembled with zinc electrode sheets of examples 1-3;
fig. 5 is an EIS graph of a symmetric cell assembled with zinc electrode tabs in examples 1-3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is to modify a layer of coating material with high specific surface area and zinc affinity on the surface of the zinc cathode, the modified interface can enhance the diffusion kinetics of zinc ions and reduce the nucleation overpotential of zinc, promote the uniform deposition of zinc ions, inhibit the growth of dendrites and reduce the occurrence of polarization and side reaction, thereby improving the cycle performance of the battery.
The related embodiments of the invention are:
example 1
The embodiment comprises the following steps:
1) Preparation of Zinc cathode Material
The zinc sheet is pretreated. Preparing 0.02mol/L dilute hydrochloric acid, putting zinc foil into the dilute hydrochloric acid, performing ultrasonic treatment for 2 minutes, washing with deionized water for 4 times to remove the residual dilute hydrochloric acid, and performing ultrasonic treatment with ethanol for 2 minutes. The zinc foil treated by the method is naturally dried in the room temperature environment for standby. The above purpose is to remove the oxide layer and surface impurities generated in the air of the zinc foil.
2) Assembled symmetrical battery
Cutting the zinc anode material prepared in the step 1) into electrode plates with the diameter of 12mm by using a slicer, wherein two identical electrode plates are used as positive electrode plates and negative electrode plates. A piece of zinc negative electrode plate is firstly placed in the positive electrode shell, one surface with a coating is ensured to contact the diaphragm, and then the glass fiber diaphragm is placed. 120uL 2mol/L ZnSO is added dropwise 4 And taking the solution as electrolyte, then putting another zinc negative electrode plate above the diaphragm, enabling one surface with the coating to contact the diaphragm, then sequentially putting a gasket and an elastic sheet, finally buckling a negative electrode shell, and packaging the battery by a battery packaging machine to obtain a modified zinc negative electrode water system zinc ion symmetrical button battery, wherein the zinc// Zn symmetrical battery is marked.
Example 2
The embodiment comprises the following steps:
1) Preparation of Zinc cathode Material
And (3) weighing 0.8g of terephthalic acid, putting the terephthalic acid into a porcelain boat, heating to 500 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours to obtain a black product carbon material, mixing 90mg of Cu@C and 10mg of polyvinylidene fluoride, grinding, adding the mixture into N-methylpyrrolidone, and stirring at room temperature for 8 hours to form a modified layer slurry. And coating the prepared slurry on the surface of a zinc cathode, and vacuum drying for 8 hours at 60 ℃ to obtain the Zn-C pole piece.
2) Assembled symmetrical battery
Two Zn-C pole pieces are assembled into a symmetrical battery, and the electrolyte used is ZnSO of 2mol/L 4 The solution was tested for electrochemical performance.
Example 3
The embodiment comprises the following steps:
1) Preparation of Zinc cathode Material
1.8g of copper nitrate and 0.8g of polyvinylpyrrolidone were weighed into 100mL of methanol, 0.8g of terephthalic acid was also dissolved in 100mL of methanol, and after stirring uniformly, the two solutions were mixed, stirred for 10min and aged.
After aging for 24 hours, the precipitate is washed with methanol, centrifuged and dried in vacuum at 120 ℃ for 12 hours;
and (3) placing the dried product into a porcelain boat, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the product Cu@C.
90mg of Cu@C and 10mg of polyvinylidene fluoride are weighed, mixed, ground and added into N-methylpyrrolidone, and stirred at room temperature for 8 hours to form a modified layer slurry. And coating the prepared slurry on the surface of a zinc cathode, and vacuum drying for 8 hours at 60 ℃ to obtain the Zn-Cu@C pole piece.
2) Assembled symmetrical battery
Two Zn-Cu@C pole pieces are assembled into a symmetrical battery, and the electrolyte used is ZnSO of 2mol/L 4 The solution was tested for electrochemical performance.
Electrochemical performance testing of the symmetric cell assembled from the cathodes of the two examples, modification of the interface increased the cycle life of the cell, and example 3 at 3mA cm -2 The zinc anode can still circulate for 700 hours under the high current density, and keeps lower polarization, and the unmodified zinc anode can only circulate for a short time, so that the results show that the feasibility of interface modification and Cu@C can obviously improve the electrochemical performance of the battery.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form 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 understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A method for preparing a zinc anode material with high specific surface area and zinc affinity, which is characterized by comprising the following steps:
1) Adding copper nitrate and polyvinylpyrrolidone into a methanol solution, dissolving terephthalic acid into the methanol solution, stirring at room temperature for a period of time, adding a copper nitrate and polyvinylpyrrolidone mixed solution into the terephthalic acid solution, and stirring at room temperature to obtain a mixed solution;
2) Aging the prepared mixed solution at room temperature to generate a precipitate;
3) Washing the obtained precipitate with methanol, centrifuging, and vacuum drying to obtain blue powder;
4) Placing blue powder into a porcelain boat, heating to 400-700 ℃ in a tube furnace at a certain heating rate under argon atmosphere, preserving heat for a period of time, and naturally cooling to room temperature to obtain an intermediate product Cu@C;
5) Adding an intermediate product Cu@C and polyvinylidene fluoride white powder into an organic solvent according to the mass ratio of 8-10:1, and stirring at room temperature to obtain zinc metal negative electrode modification layer slurry;
6) And coating the zinc metal negative electrode modification layer slurry on zinc foil, and vacuum drying to obtain the Zn-Cu@C pole piece.
2. The preparation method according to claim 1, wherein in the step 1), the mass ratio of copper nitrate, polyvinylpyrrolidone and terephthalic acid is: 0.5 to 1: 0.2-0.6:0.3-0.7.
3. The method according to claim 1, wherein in step 1), the stirring speed is 300 to 500r/min and the stirring time is 5 to 15min.
4. The method according to claim 1, wherein in step 2), the aging time is 12 to 24 hours.
5. The method according to claim 1, wherein in step 3), the vacuum drying temperature is 60 to 80 ℃ and the drying time is 8 to 12 hours.
6. The method according to claim 1, wherein in the step 4), the temperature rising rate is 1-5 ℃/min and the heat preservation time is 2-5 h.
7. The process according to claim 1, wherein in step 5), the organic solvent is N-methylpyrrolidone, and the stirring time is 6 to 8 hours.
8. The method according to claim 1, wherein in step 6), the vacuum drying temperature is 60 to 80 ℃ and the drying time is 6 to 12 hours, and the coating method is a knife coating method.
9. A zinc anode material having a high specific surface area and a zinc philicity, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the zinc anode material according to claim 9 for preparing an aqueous zinc ion battery anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311520686.2A CN117317122A (en) | 2023-11-15 | 2023-11-15 | Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311520686.2A CN117317122A (en) | 2023-11-15 | 2023-11-15 | Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117317122A true CN117317122A (en) | 2023-12-29 |
Family
ID=89260576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311520686.2A Pending CN117317122A (en) | 2023-11-15 | 2023-11-15 | Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117317122A (en) |
-
2023
- 2023-11-15 CN CN202311520686.2A patent/CN117317122A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113054165B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN112582578B (en) | Zinc cathode with protective layer and preparation method and application thereof | |
| CN113258070B (en) | Metal zinc cathode interface modification method for water-based zinc ion battery | |
| CN115799512A (en) | Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth | |
| CN113013418A (en) | Alloy framework supported zinc metal cathode and preparation method and application thereof | |
| CN113690397B (en) | Zinc cathode pole piece and preparation method and application thereof | |
| CN112928343B (en) | Water system copper ion battery suitable for large-scale energy storage application | |
| CN112242571B (en) | Electrolyte for protecting zinc ion battery electrode and zinc ion battery | |
| CN113871624A (en) | Zinc cathode coating material for water system zinc ion battery and preparation method and application thereof | |
| CN115064651B (en) | Double-functional protective layer modified zinc anode and preparation method thereof | |
| CN115881915A (en) | Large-scale preparation method for in-situ construction of zinc cathode metal composite protective layer by ultrafast microwave technology and application thereof | |
| CN114243019A (en) | Zinc cathode material with double modification layers on surface, preparation method thereof and application of zinc cathode material in water-based zinc ion battery | |
| CN111446509B (en) | Electrolyte and gel electrolyte for secondary zinc ion battery and preparation method thereof | |
| CN115010941A (en) | Preparation method and application of ionic covalent organic framework nanosheet protective layer through electrodeposition | |
| CN117317122A (en) | Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof | |
| CN114447445A (en) | Preparation and application of aqueous zinc ion battery electrolyte | |
| CN105826542B (en) | A kind of copper-antimony alloy-antimony nucleocapsid structure material and its application | |
| CN115020683B (en) | Preparation method of TAP/Ti3C2Tx electrode material | |
| CN116130795A (en) | Electrolyte additive and application thereof in water-based zinc ion battery | |
| CN114824151A (en) | Metal zinc cathode protected by chemical passivation layer and preparation method and application thereof | |
| CN117410436A (en) | Preparation method of metal zinc negative electrode protective layer of water-based zinc ion battery | |
| CN117276697A (en) | Electrolyte for zinc ion battery and preparation method and application thereof | |
| CN117458001A (en) | Application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as electrolyte cosolvent in water-based zinc ion battery | |
| CN114388903A (en) | Organic additive-containing electrolyte for water-based zinc ion battery, preparation method of organic additive-containing electrolyte and water-based zinc ion battery | |
| CN117691035A (en) | Zinc ion battery negative electrode material prepared by in-situ growth of metal-organic framework and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |