CN112349873B - Method for improving cycling stability of zinc cathode of water-based zinc ion battery and application of method - Google Patents

Method for improving cycling stability of zinc cathode of water-based zinc ion battery and application of method Download PDF

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CN112349873B
CN112349873B CN202011223110.6A CN202011223110A CN112349873B CN 112349873 B CN112349873 B CN 112349873B CN 202011223110 A CN202011223110 A CN 202011223110A CN 112349873 B CN112349873 B CN 112349873B
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CN112349873A (en
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方国赵
梁叔全
周苗
胡云智
罗雄宾
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Central South University
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    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/56—Elongation control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C31/00—Control devices, e.g. for regulating the pressing speed or temperature of metal; Measuring devices, e.g. for temperature of metal, combined with or specially adapted for use in connection with extrusion presses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
    • B22D25/04—Casting metal electric battery plates or the like
    • 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
    • H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
    • H01M4/0485—Casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B2265/00—Forming parameters
    • B21B2265/10—Compression, e.g. longitudinal compression
    • 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

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Abstract

The invention discloses a method for improving the cycling stability of a zinc cathode of a water system zinc ion battery and application thereof, wherein the method comprises the following steps: rolling, namely rolling the zinc sheet for multiple times to obtain a zinc plate with the thickness of 0.03-1.0 mm, wherein the number of times is not less than 3, and the deformation of each time in the last three times of rolling is not less than 35%; extruding, namely extruding the as-cast cylindrical zinc ingot to obtain a zinc plate with the thickness of 1-40 mm, wherein the extrusion ratio is not less than 8.72; and (3) casting, namely pouring the molten zinc into a pure copper water-cooled mold to obtain a zinc plate with the thickness of not less than 30mm, wherein the heat conductivity coefficient of the mold is not less than 400 w/m.k. According to the invention, the pole density of (002) crystal face in the zinc cathode reaction interface is increased to be not less than 14.44 by strict and fine process regulation in the zinc cathode processing process, so that the cycling stability of the zinc cathode of the water system zinc ion battery is improved.

Description

Method for improving cycling stability of zinc cathode of water-based zinc ion battery and application of method
Technical Field
The invention belongs to the technical field of water-system zinc ion batteries, and relates to a method for improving the cycling stability of a zinc cathode of a water-system zinc ion battery and application thereof, wherein the polar density of a (002) surface of the zinc cathode is not lower than 14.44 through a processing technology, so that the cycling stability of the zinc cathode is improved.
Background
Energy diversification is one of important means for guaranteeing energy safety in China, expands the application to electricity, reduces the dependence on mineral energy, particularly the dependence on imported petroleum, and has a key role. Along with the increase of energy gaps, the development, the manufacture and the improvement of the optimized battery performance are very urgent. The water system zinc ion battery is taken as a chargeable and dischargeable energy storage device, has wide attention due to the advantages of good safety, no toxicity, high energy density, high power density, low cost and the like, has potential application value and development prospect, and is a hot direction of current research.
The zinc metal has large reserve, wide source and low price. It is more attractive that the zinc ions are divalent in charge so that the battery can provide higher storage capacity. However, zinc negative electrodes have problems of zinc dendrites, dead zinc, side reactions (hydrogen evolution, corrosion, negative products), and the like during charge and discharge cycles. In order to solve this problem, some solutions have been proposed, such as: the technical scheme includes a foamed zinc electrode, graphene doping, superfine zinc powder doping, rare earth doping and the like, and the technical scheme solves the problems of zinc dendrite, dead zinc and the like to a certain extent, but undoubtedly greatly improves the production cost and greatly limits the large-scale application quality and prospect of the zinc electrode.
Disclosure of Invention
Aiming at the problems of zinc dendrite, dead zinc, side reaction and the like existing in the charge-discharge cycle of a zinc cathode in the prior art, the invention aims to provide a method for improving the cycle stability of the zinc cathode of a water system zinc ion battery and application thereof, and the pole density of (002) crystal face in a zinc cathode reaction interface is increased to be not less than 14.44 through strict and fine process regulation in the processing process of the zinc cathode, so that the cycle stability of the zinc cathode of the water system zinc ion battery is improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for improving the cycling stability of a zinc cathode of a water system zinc ion battery comprises the following steps:
the first scheme is as follows: rolling of
Rolling the zinc sheet for multiple times to obtain a zinc plate, wherein the number of times is not less than 3, and the deformation of each time in the last three times of rolling is not less than 35%;
scheme II: extrusion
Extruding the cast cylindrical zinc ingot to obtain a zinc plate, wherein the extrusion ratio (the extrusion ratio is the ratio of the cross section area of an extrusion cylinder cavity to the total cross section area of an extruded product, also called the extrusion coefficient) is not less than 8.72;
the third scheme is as follows: casting
Pouring the zinc melt into a pure copper water-cooled mold to obtain the zinc plate, wherein the heat conductivity coefficient of the mold is not less than 400 w/m.k.
Preferably, in the first scheme, the thickness of the zinc sheet is 2-30 mm, and the thickness of the prepared zinc sheet is 0.03-1.0 mm.
Preferably, in the second scheme, the diameter of the cylindrical zinc ingot is 50-500 mm, and the thickness of the prepared zinc plate is 1-40 mm.
Preferably, in the third scheme, the temperature of the zinc melt is not lower than 500 ℃, and the thickness of the prepared zinc plate is not less than 30 mm.
Preferably, the pole density of the (002) plane of the zinc negative electrode is not less than 14.44.
The invention also provides application of the zinc cathode, and the zinc cathode is applied to an aqueous zinc ion battery.
According to the invention, the pole density of (002) crystal face in the reaction interface of the zinc cathode is increased to be not lower than 14.44 through strict and fine process regulation in the processing process of the zinc cathode, so that the formation of dendrite on the reaction interface can be inhibited, the reversibility and the coulombic efficiency are improved, and the electrochemical performance of the battery is effectively improved.
The invention has the advantages that:
the invention adopts three simple processing technologies, and the pole density of the (002) surface of the zinc cathode is not lower than 14.44 by strict and fine process regulation in the processing process, so that the reaction interface of the zinc cathode is improved. Compared with other existing means, the method has the advantages that the practicability is strong, the cost is low, the method can be quickly applied to commercial production, the improved zinc cathode cannot form large dendritic crystals during discharging, the dendritic crystals are prevented from penetrating a diaphragm, the reversibility and the coulombic efficiency are improved, and the safe operation and the service life of the battery are ensured.
Drawings
Fig. 1 is an XRD pattern before cycling of the zinc negative electrode (Zn (002)) obtained in example 1 and the ordinary zinc sheet (Zn (100)) of comparative example 1, and the electrode density of the corresponding texture;
fig. 2 is a graph showing the comparison of cycle performance of the zinc negative electrode (Zn (002)) obtained in example 1 with the conventional zinc sheet (Zn (100)) of comparative example 1 for a zinc/zinc symmetrical cell (a), an XRD pattern after cycling for a symmetrical cell (b), and a coulombic efficiency comparison pattern after cycling for a zinc/copper asymmetrical cell (c);
FIG. 3 is an XRD pattern (a), texture (b) and a zinc symmetric battery cycle chart (c) before cycle of the zinc cathode obtained in comparative example 2;
FIG. 4 is a graph showing the nucleation overpotential (a), the alternating current impedance (EIS) (b) and the Linear Sweep Voltammograms (LSV) (c) and (d) of the zinc negative electrode (Zn (002)) obtained in example 1 and the conventional zinc sheet (Zn (100)) of comparative example 1;
FIG. 5 is a graph showing the performance of the zinc negative electrode (Zn (002)) obtained in example 1, and the conventional zinc sheet (Zn (100)) of comparative example 1, using different positive electrodes, (a) manganese dioxide and (b) ammonium vanadate;
fig. 6 is SEM and XPS images of a zinc/zinc symmetric cell after cycling, (a) the zinc negative electrode obtained in example 1 (Zn (002)), (b) the common zinc flake of comparative example 1 (Zn (100)).
Fig. 7 is XRD patterns before cycling of zinc anodes obtained in example 2(a and b) and comparative examples 3(c and d) and the pole densities of the corresponding textures;
fig. 8 is an XRD pattern before cycle of the zinc negative electrodes obtained in example 3(a and b) and comparative example 4(c and d) and the pole density of the corresponding texture.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative of the invention and are not intended to be limiting, and the starting materials of the invention are commercially available, and the methods of preparation of the invention are conventional in the art unless otherwise specified.
Example 1
The preparation method of the zinc cathode with the pole density of (002) surface of 14.44 provided by the embodiment of the invention comprises the following steps:
(1) preparing a pure zinc sheet with the length of 200mm, the width of 100mm and the thickness of 2mm, and marking as a zinc sheet A;
(2) and (3) preheating the zinc sheet A in a heating furnace, raising the temperature to 210 ℃, and preserving the temperature for 30 min. The working rolls of the rolling mill are adjusted to the interval of 1.3mm and the rotating speed is 400 r/min. Taking out the preheated zinc sheet A, and rolling along the direction vertical to the short axis to obtain a zinc sheet with the length of 200mm, the width of 135mm and the thickness of 1.3mm, wherein the deformation amount is 35 percent and is marked as a zinc sheet B;
(3) and (3) preheating the zinc sheet B in a heating furnace, raising the temperature to 170 ℃, and preserving the temperature for 20 min. The working rolls of the rolling mill are adjusted to 0.8mm space and the rotating speed is 600 r/min. Taking out the preheated zinc sheet B, and rolling along the direction vertical to the short axis to obtain a zinc sheet with the length of 200mm, the width of 187mm and the thickness of 0.8mm, wherein the zinc sheet C is marked as the deformation of 38.5 percent;
(4) and (3) preheating the zinc sheet C in a heating furnace, raising the temperature to 120 ℃, and preserving the temperature for 10 min. The working rolls of the rolling mill are adjusted to 0.5mm space and rotate at the speed of 800 r/min. Taking out the preheated zinc sheet C, and rolling along the direction vertical to the short axis to obtain a zinc sheet with the length of 200mm, the width of 257mm and the thickness of 0.5mm, wherein the deformation is 37.5%. Finally, the zinc cathode with the pole density of 14.44 on the two (002) surfaces of the zinc sheet is obtained, and both the two surfaces of the zinc sheet can be used as the reaction surfaces of the battery.
Comparative example 1
Comparative example 1 is a conventional zinc plate (Zn (100)) which was purchased from Weifang Purun Limited and had a zinc content of 99.9% or more.
Comparative example 2
(1) Preparing a pure zinc sheet with the length of 200mm, the width of 100mm and the thickness of 2mm, and marking as a zinc sheet A;
(2) and (3) preheating the zinc sheet A in a heating furnace, raising the temperature to 210 ℃, and preserving the temperature for 30 min. The working rolls of the rolling mill are adjusted to the interval of 1.5mm and the rotating speed is 400 r/min. Taking out the preheated zinc sheet A, and rolling along the direction vertical to the short axis to obtain a zinc sheet with the length of 200mm, the width of 125mm and the thickness of 1.5mm, wherein the deformation amount is 25 percent and is marked as a zinc sheet B;
(3) and (3) preheating the zinc sheet B in a heating furnace, raising the temperature to 170 ℃, and preserving the temperature for 20 min. The working rolls of the rolling mill are adjusted to the interval of 1.2mm and the rotating speed is 500 r/min. Taking out the preheated zinc sheet B, and rolling along the direction vertical to the short axis to obtain a zinc sheet with the length of 200mm, the width of 150mm and the thickness of 1.2mm, wherein the zinc sheet C is marked as the deformation of 20 percent;
(4) and (3) preheating the zinc sheet C in a heating furnace, raising the temperature to 120 ℃, and preserving the temperature for 10 min. The working rolls of the rolling mill are adjusted to 0.8mm space and the rotating speed is 600 r/min. The zinc sheet C after preheating was taken out and rolled in the direction perpendicular to the minor axis to obtain a zinc sheet having a length of 200mm, a width of 187mm and a thickness of 0.8mm, and a deflection of 33.3%. Finally, the zinc negative electrode with the pole density of 11.81 on the two (002) surfaces of the zinc sheet is obtained.
As shown in fig. 1, the XRD pattern and the polar pattern before the cycles of the zinc negative electrode (Zn (002)) and the general zinc sheet (Zn (100)) obtained in example 1 are shown. The zinc negative electrode of example 1, which was calculated by the pole density formula, had a pole density of 14.44 in the (002) plane and 3.79 in the (002) plane of the ordinary zinc sheet (Zn (100)), indicating that a zinc negative electrode with more (002) planes exposed was prepared by the rolling method.
Fig. 2 is a comparison of the cycling performance of the zinc negative electrode (Zn (002)) obtained in example 1 with the conventional zinc sheet (Zn (100)) zinc/zinc symmetric cell of comparative example 1 (a), XRD pattern after cycling of the symmetric cell (b), and coulombic efficiency comparison pattern after cycling of the zinc/copper asymmetric cell (c). The Zn (002) negative electrode can be cycled for 500 hours, the voltage hysteresis is only 38mV, and the Zn (100) symmetrical battery is short-circuited in less than 50 hours; from XRD pattern, Zn (002) phase is not changed, and Zn (100) has a obvious irreversible by-product Zn4SO4(OH)6·H2The peak of the O phase (PDF #39-0690) indicates that the Zn (100) negative electrode has serious side reaction, so that the coulomb efficiency of the Zn (002) negative electrode is as high as 97.71%, and the zinc metal negative electrode is exposed to more (002) surfaces, so that the reversibility and the cycling stability of the battery can be improved, and the cycle life of the battery can be prolonged.
As shown in fig. 3, the XRD pattern (a), texture (b) and zinc symmetric cell (c) before cycling of the zinc negative electrode prepared in comparative example 2 are shown. When the rolling deformation is less than 35%, the pole density of the (002) surface of the zinc cathode is reduced to 11.82, and the pole density of the (101) surface is increased to 22.96, so that the cycle performance of the zinc/zinc symmetrical battery is rapidly reduced, the voltage is unstable after only 60 hours of cycle, and short circuit occurs after 80 hours, which shows that the zinc cathode can expose more (002) surfaces by controlling the rolling deformation, and further the reversibility and cycle life of the zinc cathode can be effectively improved.
Fig. 4 is a graph comparing the nucleation overpotential (a), the alternating current impedance (EIS) (b), and the Linear Sweep Voltammogram (LSV) (c) and (d) of the zinc negative electrode (Zn (002)) obtained in example 1 and the conventional zinc sheet (Zn (100)) of comparative example 1. The nucleation overpotential of Zn (002) is 35.3mV, which is lower than that of Zn (100) (61.7mV), and shows that the zinc metal negative electrode exposes more (002) surface and is beneficial to reducing the shapeNuclear overpotential, so that zinc is uniformly deposited. Compared with an EIS diagram, the charge transfer resistance of the Zn (002) symmetrical battery is 157.5 omega, and the corresponding ionic conductivity is 2.44 multiplied by 10-2S cm-1While Zn (100) has a charge transfer resistance of 198.8. omega. and an ion conductivity of 1.39X 10-2S cm-1(ii) a Comparison of the LSV chart shows that the exchange current density of Zn (002) (8.79X 10)- 5mA cm-2) 1/9 (7.89X 10) of Zn (100) only-4mA cm-2) The hydrogen evolution reaction is effectively inhibited, and the zinc metal negative electrode is shown to be capable of inducing the zinc to be uniformly deposited by exposing more (002) surfaces and inhibiting the generation of side reaction, thereby improving the electrochemical performance of the zinc negative electrode.
As shown in fig. 5, the performance of the zinc negative electrode (Zn (002)) obtained in example 1 and the normal zinc sheet (Zn (100)) of comparative example 1 were shown by using different positive electrodes, wherein (a) was manganese dioxide and (b) was ammonium vanadate. At 0.2Ag-1Zn (002)/MnO at current density2The full battery can stably circulate for 100 circles, and the capacity retention rate is as high as 94.12%; and Zn (100)/MnO2The capacity is obviously reduced, and the capacity retention rate is only 65.0 percent; at 5Ag-1Relative to Zn (100) NH at current density4V4O10Full cell, Zn (002)/NH4V4O10The cycle stability of the full battery is greatly improved, the full battery still has good capacity retention rate after standing, and the full battery can be continuously cycled for 1000 times. Furthermore, the coulombic efficiency remains stable at all times. The negative electrode can be suitable for different positive electrode materials and shows excellent stability.
Fig. 6 is SEM and XPS images of a zinc/zinc symmetric cell after cycling, (a) the zinc negative electrode obtained in example 1 (Zn (002)), (b) the common zinc flake of comparative example 1 (Zn (100)). Zn (002) has a smooth surface, zinc is uniformly deposited, while common zinc sheet Zn (100) shows obvious protrusions, zinc element is distributed intensively, and the phenomenon of zinc dendrite is shown. The zinc metal negative electrode is shown to expose more (002) surfaces, can inhibit the growth of zinc dendrites and keep better cycle performance.
Example 2
The preparation method of the zinc cathode with the pole density of the (002) surface of 24.44 in the embodiment of the invention comprises the following steps:
(1) preparing a cylindrical zinc ingot with phi of 100mm and H of 300mm, and marking as a zinc ingot A;
(2) putting the zinc ingot A into a heating furnace, preheating to 220 ℃, and preserving heat for 1h, and marking as a zinc ingot B;
(3) taking out the zinc ingot B and putting the zinc ingot B into an extrusion barrel (800 ton extruder) to obtain a long zinc strip with the thickness of 10mm and the width of 90mm, wherein the extrusion ratio is 8.72, and the polar density of (002) surfaces on two surfaces of the zinc strip is 24.44;
comparative example 3
(1) Preparing a cylindrical zinc ingot with phi of 100mm and H of 300mm, and marking as a zinc ingot A;
(2) putting the zinc ingot A into a heating furnace, preheating to 220 ℃, and preserving heat for 1h, and marking as a zinc ingot B;
(3) taking out the zinc ingot B and putting the zinc ingot B into an extrusion barrel (800 ton extruder) to obtain a long zinc strip with the thickness of 30mm and the width of 90mm, wherein the extrusion ratio is 2.9, and the polar density of (002) surfaces on both surfaces of the zinc strip is 11.04.
As shown in fig. 7, XRD patterns before cycle of the zinc negative electrodes obtained in example 2(a and b) and comparative example 3(c and d) and the pole densities of the corresponding textures are shown. In example 2, when the extrusion ratio was 8.72, the pole density of the (002) plane of the zinc negative electrode was 24.44, and the (100) plane was 5.17; in contrast, in comparative example 3, when the extrusion ratio is only 2.9, the pole density of the (002) surface of the zinc negative electrode is 11.04, and by comparing the two, it is shown that the exposure of the (002) surface of the zinc metal negative electrode can be enhanced by strictly controlling the appropriate extrusion ratio, and further, the electrochemical performance of the zinc negative electrode can be effectively improved.
Example 3
The preparation method of the zinc cathode with the pole density of the (002) surface of 22.34 provided by the embodiment of the invention comprises the following steps:
(1) preparing 10kg of pure zinc blocks, and marking as zinc blocks A;
(2) putting the zinc block A into a high-purity graphite heating furnace, heating to 500 ℃, and waiting until the zinc block A is completely melted;
(3) removing the oxide slag on the surface of the molten zinc melt, pouring the molten zinc melt into a pure copper water-cooled mold, wherein the thermal conductivity coefficient of the molten zinc melt is 400 w/m.k, so that a zinc plate with the thickness of 30cm multiplied by 15cm multiplied by 3cm is obtained, and the pole density of the double surfaces contacted with the mold is 22.34.
Comparative example 4
(1) Preparing 10kg of pure zinc blocks, and marking as zinc blocks A;
(2) putting the zinc block A into a high-purity graphite heating furnace, heating to 500 ℃, and waiting until the zinc block A is completely melted;
(3) removing the oxide slag on the surface of the molten zinc melt, pouring the molten zinc melt into a pure copper water-cooled mold, wherein the thermal conductivity coefficient of the molten zinc melt is 90 w/m.k, so that a zinc plate with the thickness of 30cm multiplied by 15cm multiplied by 3cm is obtained, and the pole density of the double surfaces contacted with the mold is 4.89.
As shown in fig. 8, in the XRD patterns before cycle and the polar densities of the corresponding textures obtained in the zinc anodes of examples 3(a and b) and comparative examples 4(c and d), in example 3, when the mold thermal conductivity is 400w/m · k, the polar density of the (002) plane of the zinc anode is 22.34, and the polar density of the (100) plane is 10.62; in contrast, in comparative example 4, when the mold thermal conductivity was 90 w/m.k, the pole density of the (002) plane of the zinc negative electrode was 4.89, and the pole density of the (100) plane was 12.18. Through the scheme, the heat conductivity coefficient of the mold is controlled, namely, the zinc melt is rapidly cooled, and the exposure of the (002) surface of the zinc metal negative electrode can be enhanced.

Claims (5)

1. A method for improving the cycling stability of a zinc cathode of a water system zinc ion battery is characterized in that:
the first scheme is as follows: rolling of
Rolling the zinc sheet for multiple times to obtain a zinc plate, wherein the number of times is not less than 3, and the deformation of each time in the last three times of rolling is not less than 35%;
scheme II: extrusion
Extruding the cast cylindrical zinc ingot to prepare a zinc plate, wherein the extrusion ratio is not less than 8.72;
the extrusion ratio is defined as the ratio of the cross-sectional area of the extrusion barrel cavity to the total cross-sectional area of the extruded product;
the third scheme is as follows: casting
Pouring the molten zinc into a pure copper water-cooled mold to prepare a zinc plate, wherein the heat conductivity coefficient of the mold is not less than 400 w/m.k;
the polar density of the (002) face of the zinc plate is not less than 14.44.
2. The method of claim 1, wherein the method comprises the following steps: in the first scheme, the thickness of the zinc sheet is 2-30 mm, and the thickness of the prepared zinc sheet is 0.03-1.0 mm.
3. The method of claim 1, wherein the method comprises the following steps: in the second scheme, the diameter of the cylindrical zinc ingot is 50-500 mm, and the thickness of the prepared zinc plate is 1-40 mm.
4. The method of claim 1, wherein the method comprises the following steps: in the third scheme, the temperature of the molten zinc is not lower than 500 ℃, and the thickness of the prepared zinc plate is not less than 30 mm.
5. The application of the zinc plate prepared by the method for improving the cycling stability of the zinc cathode of the aqueous zinc ion battery according to any one of claims 1 to 4 is characterized in that: the electrolyte is applied to an aqueous zinc ion battery.
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CN113991047B (en) * 2021-10-22 2023-04-18 哈尔滨工业大学 Preparation method and application of modified metal zinc cathode
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