CN111769251A - Method for protecting metal electrode - Google Patents

Method for protecting metal electrode Download PDF

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Publication number
CN111769251A
CN111769251A CN202010278088.9A CN202010278088A CN111769251A CN 111769251 A CN111769251 A CN 111769251A CN 202010278088 A CN202010278088 A CN 202010278088A CN 111769251 A CN111769251 A CN 111769251A
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Prior art keywords
metal
zinc
electrode
protective layer
stainless steel
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吴超
王官耀
张远俊
朱铭
张英
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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
    • 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
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • 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
    • 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 invention discloses a method for protecting a metal electrode, which adopts a physical vapor deposition method to spray metal copper or silver on the surfaces of stainless steel and metal zinc to form a compact protective layer, and simultaneously, metal generated in the electroplating process of zinc can form alloy with zinc, thereby better protecting the zinc electrode, greatly improving the coulombic efficiency of zinc and simultaneously inhibiting the generation of zinc dendrites. Has good stability under the conditions of large current and large capacity. Copper, as one of the most effective protective layers, is significantly superior to pristine zinc in terms of coulombic efficiency and symmetric cell performance. And has significant advantages in full cell applications. The invention solves the bottleneck of coulomb efficiency and zinc dendrite, and opens up a new way for the practical application of the zinc metal cathode.

Description

Method for protecting metal electrode
Technical Field
The invention relates to a preparation method of an electrode, in particular to a preparation method of a zinc electrode, belonging to the technical field of zinc batteries or zinc electrochemical devices.
Background
In recent years, the continuous consumption of fossil energy and the environmental pollution problem derived from the fossil energy are increasingly receiving attention. In order to alleviate the above problems, the development and effective utilization of renewable clean energy sources, which replace traditional energy sources such as coal, oil, and natural gas, have become important research subjects, such as solar energy and wind energy, and the development of new energy industry is becoming more and more vigorous. In recent decades, lithium ion batteries have been developed rapidly, but the problems of high price and poor lithium resources, toxic electrolyte and battery safety have attracted more and more attention, and further large-scale application of the lithium ion batteries is seriously hindered. Significant efforts are now being made to develop sodium and potassium ion batteries, but safety has always limited the development of these energy storage batteries.
Based on the above safety considerations, rechargeable batteries using aqueous electrolytes have unparalleled advantages because of their low cost, ease of assembly, high safety, and high ionic conductivity (10)-1–6S cm-1) Is superior to that in organic electrolyte (10)-3-10-2Scm-1). The aqueous zinc ion battery is considered to be expected to replace a non-aqueous lithium or sodium ion battery, mainly because of its safety and price advantage, and the positive electrode material V of the aqueous zinc ion battery2O5Raw materials (about $ 5.5 per kg) and manganese ore (about $ 0.005 per kg) are cheaper than lithium raw materials for lithium ion batteries, li (nimnco) O2Price $ 34 per kilogram, LiCoO2The price is $ 55 per kilogram. ZnSO, in contrast to organic electrolytes4/H2The price of O electrolyte is negligible, with a price of about $ 7 to $ 20 per kilogram. Zinc ion batteries cost less than $ 65/kwh and much less expensive than current lithium ion batteries, $ 300/kwh. Furthermore, multivalent aqueous zinc ion batteries that allow for the transfer of multiple electrons during electrochemical reactions offer the opportunity to achieve high energy and high power densities.
The study of aqueous zinc ion batteries dates back to 1986 when Yamamoto et al first replaced the alkaline electrolyte with zinc sulfate electrolyte and started rechargeable Zn | ZnSO4| MnO2 batteriesThe electrochemical behavior of (a). In recent years, aqueous zinc ion batteries have attractive properties of environmental friendliness, safety, convenience in assembly in air, low cost and high capacity, and have attracted a lot of interest again, including the search for zinc negative electrode, electrolyte and positive electrode materials. However, there are many difficult to estimate challenges in the development of electrodes and even entire battery systems, all of which need to be considered. Published articles on aqueous zinc ion batteries are more inclined to the recent advances in the construction of electrode materials, electrolytes and energy storage mechanisms than to face these problems and give potential solutions to aqueous zinc ion batteries, the negative electrode being very soluble, the adverse effects of electrostatic interactions, by-products, zinc dendrites, corrosion and passivation. Wherein the zinc metal cathode has a lower potential (-0.76V compared to the standard hydrogen potential) and a high theoretical capacity (820 mAhg)-1). However zinc dendrites are a key issue limiting the application of metallic zinc anodes. How to overcome the problems of zinc dendrites and the utilization rate of zinc of the negative electrode and provide a reasonable solution for the implementation of the zinc negative electrode becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for protecting a metal electrode.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method of protecting a metal electrode, comprising the steps of:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel or metal zinc material as electrode base material, directly spraying protective layer metal on the surface of the stainless steel or metal zinc by using a physical vapor deposition method, and respectively forming metal protective layers with the thickness of 90-300 nanometers on the surfaces of the stainless steel or metal zinc;
b. preparing an electrode assembly:
cutting the metal zinc or the stainless steel for preparing the protective layer in the step a into metal zinc sheets or stainless steel sheets with the diameter not less than 10 millimeters, and using the metal zinc sheets or the stainless steel sheets as electrodes of symmetrical batteries and working electrodes in coulombic efficiency tests for standby;
c. surface alloying process of electrode assembly:
b, taking the metal zinc sheet or the stainless steel sheet cut in the step b as an electrode of a symmetrical battery or a working electrode in a coulombic efficiency test, adopting an aqueous electrolyte, wherein the electrolyte is a zinc sulfate solution with the concentration of not less than 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is not less than 0.1 mol per liter; the electrode, the diaphragm and the electrolyte are assembled into an electrolytic device or a battery device, and when the first electrochemical reaction is carried out, an electroplating process is carried out on the surface of the electrode, so that the protective layer metal on the surface of the electrode and the electroplated zinc are subjected to an alloying process, and an alloy layer is formed on the protective layer. Can effectively induce the subsequent deposition of zinc.
In a preferred embodiment of the present invention, in the step a, the protective layer metal is made of one or two metal materials selected from copper and silver.
As a preferred technical solution of the present invention, in the step a, when the protective layer metal is copper, the physical vapor deposition temperature for preparing the metal protective layer by physical vapor deposition is 1200-1400 ℃, and the thickness is not more than 300 nm.
As a preferable technical scheme of the invention, in the step a, when the protective layer metal adopts silver, the physical vapor deposition temperature for preparing the metal protective layer by physical vapor deposition is 850-1200 ℃, and the thickness is not more than 170 nm.
As a preferred technical solution of the present invention, in the step a, when the physical vapor deposition is performed to prepare the metal protective layer, the pressure of the atmosphere for performing the physical vapor deposition is controlled to be not more than 10-4Pa。
In a preferred embodiment of the present invention, in the step c, glass fibers are used as the material of the separator.
As a preferred technical solution of the present invention, in the step c, the alloy layer on the surface of the electrode can also be used as a composite material for reducing the nucleation resistance of zinc and inducing the uniform deposition of zinc.
Compared with the prior art, the invention has the following prominent substantive characteristics and remarkable advantages:
1. the metal protective layer prepared by the method can react with zinc to generate alloy in the electroplating process of the zinc, and the alloy can well reduce the nucleation resistance of the zinc and induce the uniform deposition and separation of the zinc, so that the coulombic efficiency of the battery is greatly improved, and the generation of zinc dendrite is inhibited;
2. the method forms the alloy layer on the zinc surface in situ, greatly improves the coulomb efficiency of the zinc cathode, and has good stability under the conditions of large current and large capacity;
3. the method solves the bottleneck of coulomb efficiency and zinc dendrite, and opens up a new way for the practical application of the zinc metal cathode.
4. The method has simple process, easy realization and very obvious economic benefit.
Drawings
FIG. 1 is an SEM image of an electrode prepared by the method of example 1 of the present invention.
FIG. 2 is an SEM image of an electrode prepared by the method of example 2 of the present invention.
FIG. 3 is an SEM image of an electrode prepared by the method of example 3 of the invention.
FIG. 4 is an SEM image of an electrode prepared by the method of example 4 of the invention.
FIG. 5 is an XRD pattern of an electrode prepared by the method of example 5 of the present invention.
FIG. 6 is a diagram showing the overpotential curve of an electrode prepared by the method of example 6 of the present invention.
Fig. 7 is a graph comparing the cycle performance of batteries fabricated by the method of example 7 of the present invention and the pristine stainless steel electrode.
Fig. 8 is a graph comparing the cycle performance of batteries fabricated by the method of example 8 of the present invention and the pristine stainless steel electrode.
Fig. 9 is a graph comparing the cycle performance of batteries fabricated with electrodes made of the method of example 9 of the present invention and pristine stainless steel electrodes.
Fig. 10 is a graph comparing the cycle performance of batteries fabricated with electrodes made of the method of example 10 of the present invention and pristine stainless steel electrodes.
Fig. 11 is a graph comparing the cycle performance of batteries fabricated with electrodes made of the method of example 11 of the present invention and pristine stainless steel electrodes.
Fig. 12 is a graph comparing the cycle performance of batteries fabricated by the method of example 12 of the present invention and the pristine stainless steel electrode.
Fig. 13 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 13 of the present invention and virgin metallic zinc electrodes.
Fig. 14 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 14 of the present invention and virgin metallic zinc electrodes.
Fig. 15 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 15 of the present invention and virgin metallic zinc electrodes.
Fig. 16 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 16 of the present invention and virgin metallic zinc electrodes.
Figure 17 is an XRD pattern of an electrode prepared by the method of example 17 of the present invention.
Fig. 18 is an XRD pattern of the electrode prepared by the method of example 18 of the present invention.
FIG. 19 is an SEM image of an electrode prepared by the method of example 19 in accordance with the present invention.
FIG. 20 is an SEM image of an electrode prepared by the method in example 20 of the invention.
FIG. 21 is an SEM image of an electrode prepared by the method of example 21.
Fig. 22 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 22 of the present invention and virgin metallic zinc electrodes.
Fig. 23 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 23 of the present invention and virgin metallic zinc electrodes.
Fig. 24 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 24 of the present invention and virgin metallic zinc electrodes.
Fig. 25 is a graph comparing the cycling performance of cells made with electrodes made by the method of example 25 of the present invention and virgin metallic zinc electrodes.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly adding silver metal at 850 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the stainless steel under Pa;
b. scanning Electron Microscope (SEM) sample preparation:
cutting the stainless steel with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, taking the stainless steel wafer as an SEM sample, and testing the surface appearance;
c. scanning Electron Microscope (SEM) sample testing:
the test is carried out by a Hitach model S4800 instrument, and the voltage is 10 KV.
The sample tests of the present example were all performed in an atmospheric environment. Samples were prepared for testing in this example and the results are shown in FIG. 1.
Example 2:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly adding silver metal at 850 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the stainless steel under Pa;
b. scanning Electron Microscope (SEM) sample preparation:
b, shearing the stainless steel with scissors to form small sheets serving as SEM samples, and testing the thickness of the metal silver layer on the surface;
c. scanning Electron Microscope (SEM) sample testing:
the test is carried out by a Hitach model S4800 instrument, and the voltage is 10 KV.
The sample tests of the present example were all performed in an atmospheric environment. Samples were prepared for testing in this example and the results are shown in FIG. 2.
Example 3:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly making copper metal at 1220 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the stainless steel under Pa;
b. scanning Electron Microscope (SEM) sample preparation:
cutting the stainless steel with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, taking the stainless steel wafer as an SEM sample, and testing the surface appearance;
c. scanning Electron Microscope (SEM) sample testing:
the test is carried out by a Hitach model S4800 instrument, and the voltage is 10 KV.
The sample tests of the present example were all performed in an atmospheric environment. Samples were prepared for testing in this example and the results are shown in FIG. 3.
Example 4:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly making copper metal at 1220 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the stainless steel under Pa;
b. scanning Electron Microscope (SEM) sample preparation:
b, shearing the stainless steel with scissors to form small sheets serving as SEM samples, and testing the thickness of the metal silver layer on the surface;
c. scanning Electron Microscope (SEM) sample testing:
the test is carried out by a Hitach model S4800 instrument, and the voltage is 10 KV.
The sample tests of the present example were all performed in an atmospheric environment. Samples were prepared for testing in this example and the results are shown in FIG. 4.
Example 5:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly making copper metal at 1220 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
directly adding silver metal at 850 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b.X ray diffraction (XRD) sample preparation:
cutting the metal zinc prepared into the protective layer in the step a into a metal zinc wafer with the diameter of 10mm by using a die, and taking the metal zinc wafer as an XRD sample;
c.X ray diffraction (XRD) test:
the test was carried out using a Rigaku D/MAX2200V PC model instrument at an angle ranging from 30 to 80 degrees and at a test speed of 8 degrees per minute.
The sample tests of the present example were all performed in an atmospheric environment. The samples prepared in this example were tested and the results are shown in FIG. 5.
Example 6:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
directly making copper metal at 1220 deg.C and 10 deg.C by physical vapor deposition-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
directly adding silver metal at 850 deg.C and 10 deg.C by physical vapor deposition-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel with the protective layer prepared in the step a into a wafer with the diameter of 10mm by using a die, and using the wafer as an electrode for later use;
c. and (3) electrode overpotential test:
b, taking the stainless steel sheet cut in the step b as a working electrode, taking metal zinc as a counter electrode, putting the counter electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2The current density and the plating time were one hour. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 6.
Example 7:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and directly making metal copper at 1220 deg.C and 10 deg.C by physical vapor deposition method-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2Capacity of (2) test coulombic efficiency. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 7.
Example 8:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and directly making metal copper at 1220 deg.C and 10 deg.C by physical vapor deposition method-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with 10mA/cm-2Current density of 1mAh/cm-2Capacity of (2) test coulombic efficiency. Electricity prepared for this exampleThe cell samples were tested and the results are shown in figure 8.
Example 9:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and directly making metal copper at 1220 deg.C and 10 deg.C by sputtering method-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with 10mA/cm-2Current density of 3mAh/cm-2Capacity of (2) test coulombic efficiency. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 9.
Example 10:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and utilizing physical vapor depositionThe method (2) directly subjecting copper metal to a treatment at 1220 ℃ and 10 DEG C-4Performing physical vapor deposition on the surface of the stainless steel under Pa to form a metal protective layer with the thickness of 300 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions and the test conditions were selected to be 50mA/cm-2Current density of 5mAh/cm-2Capacity of (2) test coulombic efficiency. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 10.
Example 11:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and utilizing physical vapor deposition method to directly make metal silver be at 860 deg.C and 10 deg.C-4Performing physical vapor deposition on the surface of stainless steel under Pa to form a metal protective layer with the thickness of 170 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with 10mA/cm-2Current density of 1mAh/cm-2Capacity of (2) test coulombic efficiency. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 11.
Example 12:
this embodiment is substantially the same as embodiment 11, and is characterized in that:
in this embodiment, a method for protecting a metal stainless steel electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel material as electrode base material, and utilizing physical vapor deposition method to directly make metal silver be at 860 deg.C and 10 deg.C-4Performing physical vapor deposition on the surface of stainless steel under Pa to form a metal protective layer with the thickness of 170 nanometers on the surface of the stainless steel;
b. preparing an electrode assembly:
cutting the stainless steel foil with the protective layer prepared in the step a into a stainless steel wafer with the diameter of 10mm by using a die, and using the stainless steel wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the stainless steel sheet cut in the step b as an electrode, putting the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with 10mA/cm-2Current density of 3mAh/cm-2Capacity of (2) test coulombic efficiency. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 12.
Example 13:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is adopted as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal copper at the temperature of 1220 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The capacity of (a) was measured for a symmetric cell polarization curve. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 13.
Example 14:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
using metallic zinc materialAs the electrode base material, the metal copper is directly treated by a physical vapor deposition method at 1220 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under test conditions of 3mA/cm in atmospheric environment-2Current density of 3mAh/cm-2The capacity of (a) was measured for a symmetric cell polarization curve. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 14.
Example 15:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is used as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal silver at 860 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 90 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The capacity of (a) was measured for a symmetric cell polarization curve. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 15.
Example 16:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is used as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal silver at 860 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 90 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under test conditions of 3mA/cm in atmospheric environment-2Current density of 3mAh/cm-2The capacity of (a) was measured for a symmetric cell polarization curve. The test was performed on the battery sample prepared in this example, and the results are shown in fig. 16.
Example 17:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is adopted as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal copper at the temperature of 1220 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The capacity measurement of the battery is carried out in a symmetrical battery test cycle, and the working electrode is taken out for XRD test after two cycles of the cycle. The test was performed on the battery sample prepared in this example, and the result is shown in fig. 17.
Example 18:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is used as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal silver at 860 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 90 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
c. the preparation process of the battery comprises the following steps:
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The capacity measurement of the battery is carried out in a symmetrical battery test cycle, and the working electrode is taken out for XRD test after two cycles of the cycle. The test was performed on the battery sample prepared in this example, and the result is shown in fig. 18.
Example 19:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
preparing an electrode assembly:
cutting the zinc foil into zinc wafers with the diameter of 10mm by using a die, and using the zinc wafers as electrodes for later use;
the cut zinc sheet is used as an electrode and is placed in a CR2032 battery case, glass fiber is used as a diaphragm, water system electrolyte is used, the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, manganese sulfate is also added into the electrolyte, and the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this embodiment was assembled under the atmospheric environment under the test conditions selected to be 1mA/cm-2Current density of 1mAh/cm-2The surface topography of the working electrode after 50h of cycling was observed by cycling tests. The results are shown in FIG. 19.
Example 20:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is used as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal silver at 860 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 170 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The surface topography of the working electrode after 100h of cycling was observed by cycling tests. The results are shown in FIG. 20.
Example 21:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for protecting a zinc metal electrode includes the following steps:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is adopted as the electrode base materialThe material is prepared by directly depositing metal copper at 1220 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
b, taking the zinc sheet cut in the step b as an electrode, placing the electrode into a CR2032 battery case, taking glass fiber as a diaphragm, taking water-based electrolyte, wherein the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under the atmospheric conditions with a test condition of 1mA/cm-2Current density of 1mAh/cm-2The surface topography of the working electrode after 100h of cycling was observed by cycling tests. The results are shown in FIG. 21.
Example 22:
in this embodiment, a full battery of protected metallic zinc includes the steps of:
a. MnO as positive electrode material2The preparation of (1):
30ml of 0.1 mol per liter KMnO4The solution was mixed with 30ml of 0.6 mol/l MnSO4·H2Mixing the O solution, adding the mixture into a hydrothermal reaction kettle, heating the mixture for 12 hours at 140 ℃, and filtering and drying the mixture;
b. preparing an electrode assembly:
cutting the zinc foil into zinc wafers with the diameter of 10mm by using a die, and using the zinc wafers as electrodes for later use;
MnO in a2Uniformly mixing with PVDF (dissolved in NMP) and conductive carbon according to the mass ratio of 8:1:1, coating on a stainless steel substrate, vacuum heating at 80 ℃ for 10 hours, and cutting into electrode slices with the diameter of 10mm by using a die for later use
Using the zinc sheet cut in said step c as a negative electrode, MnO2The pole piece is used as a positive pole and is put intoIn the CR2032 battery case, glass fiber is adopted as a diaphragm, water system electrolyte is adopted, the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, manganese sulfate is also added into the electrolyte, and the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The cell assembly of this example was tested in an atmospheric environment under test conditions selected for cycle testing at a current density of 1A/g. The results are shown in FIG. 22.
Example 23:
in this embodiment, a full battery of protected metallic zinc includes the steps of:
a. preparing a metal protective layer on the surface of an electrode material:
the metal zinc material is adopted as the electrode base material, and the physical vapor deposition method is utilized to directly deposit the metal copper at the temperature of 1220 ℃ and 10 DEG C-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. MnO as positive electrode material2The preparation of (1):
30ml of 0.1 mol per liter KMnO4The solution was mixed with 30ml of 0.6 mol/l MnSO4·H2Mixing the O solution, adding the mixture into a hydrothermal reaction kettle, heating the mixture for 12 hours at 140 ℃, and filtering and drying the mixture;
c. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
MnO in b2Uniformly mixing with PVDF (dissolved in NMP) and conductive carbon according to the mass ratio of 8:1:1, coating on a stainless steel substrate, vacuum heating at 80 ℃ for 10 hours, and cutting into electrode slices with the diameter of 10mm by using a die for later use
Using the zinc sheet cut in said step c as a negative electrode, MnO2The pole piece is used as a positive electrode and is placed in a CR2032 battery case, glass fiber is used as a diaphragm, water system electrolyte is used, the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, manganese sulfate is also added into the electrolyte, and the concentration of the manganese sulfate is 0.1 mol per liter;the battery device is assembled using the electrodes, the separator, and the electrolyte.
The cell assembly of this example was tested in an atmospheric environment under test conditions selected for cycle testing at a current density of 1A/g. The results are shown in FIG. 23.
Example 24:
in this embodiment, a full battery of protected metallic zinc includes the steps of:
a. MnO as positive electrode material2The preparation of (1):
30ml of 0.1 mol per liter KMnO4The solution was mixed with 30ml of 0.6 mol/l MnSO4·H2Mixing the O solution, adding the mixture into a hydrothermal reaction kettle, heating the mixture for 12 hours at 140 ℃, and filtering and drying the mixture;
b. preparing an electrode assembly:
cutting the zinc foil into zinc wafers with the diameter of 10mm by using a die, and using the zinc wafers as electrodes for later use;
MnO in a2Uniformly mixing with PVDF (dissolved in NMP) and conductive carbon according to the mass ratio of 8:1:1, coating on a stainless steel substrate, vacuum heating at 80 ℃ for 10 hours, and cutting into electrode slices with the diameter of 10mm by using a die for later use
Using the zinc sheet cut in said step c as a negative electrode, MnO2The pole piece is used as a positive electrode and is placed in a CR2032 battery case, glass fiber is used as a diaphragm, water system electrolyte is used, the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, manganese sulfate is also added into the electrolyte, and the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under atmospheric conditions using a cyclic test at a current density of 0.2A/g, 0.5A/g, 1A/g, 2A/g, 1A/g, 0.5A/g, 0.2A/g. The results are shown in FIG. 24.
Example 25:
in this embodiment, a full battery of protected metallic zinc includes the steps of:
a. preparing a metal protective layer on the surface of an electrode material:
adopts metallic zinc material as electrode substrateThe material is prepared by directly depositing copper at 1220 deg.C and 10 deg.C by physical vapor deposition-4Physical vapor deposition is carried out on the surface of the metal zinc under Pa, and a metal protective layer with the thickness of 300 nanometers is formed on the surface of the metal zinc;
b. MnO as positive electrode material2The preparation of (1):
30ml of 0.1 mol per liter KMnO4The solution was mixed with 30ml of 0.6 mol/l MnSO4·H2Mixing the O solution, adding the mixture into a hydrothermal reaction kettle, heating the mixture for 12 hours at 140 ℃, and filtering and drying the mixture;
c. preparing an electrode assembly:
cutting the zinc foil with the protective layer prepared in the step a into a zinc wafer with the diameter of 10mm by using a die, and using the zinc wafer as an electrode for later use;
MnO in b2Uniformly mixing with PVDF (dissolved in NMP) and conductive carbon according to the mass ratio of 8:1:1, coating on a stainless steel substrate, vacuum heating at 80 ℃ for 10 hours, and cutting into electrode slices with the diameter of 10mm by using a die for later use
Using the zinc sheet cut in said step c as a negative electrode, MnO2The pole piece is used as a positive electrode and is placed in a CR2032 battery case, glass fiber is used as a diaphragm, water system electrolyte is used, the electrolyte is zinc sulfate solution with the concentration of 3 mol per liter, manganese sulfate is also added into the electrolyte, and the concentration of the manganese sulfate is 0.1 mol per liter; the battery device is assembled using the electrodes, the separator, and the electrolyte.
The battery of this example was assembled under atmospheric conditions using a cyclic test at a current density of 0.2A/g, 0.5A/g, 1A/g, 2A/g, 1A/g, 0.5A/g, 0.2A/g. The results are shown in FIG. 25.
In view of the above-mentioned embodiments, as can be seen from fig. 1 to 25, it can be clearly seen from fig. 1 to 5 that both copper and silver are successfully sprayed on the surface of stainless steel, the surface topography is formed by combining a plurality of metal particles, and the thickness of the sprayed metal protective layer can be clearly seen. From fig. 6, it can be seen that the copper and silver protected stainless steel has a lower overpotential, which indicates that metallic zinc can be more easily deposited on the protected current collector surface during the electroplating process. FIGS. 7-12 show different current densities and capacitiesThe coulomb efficiency test of the protected stainless steel current collector shows that the coulomb efficiency of zinc on the protected stainless steel current collector is superior to that of unprotected stainless steel no matter the multiplying power is large or small, and no matter the capacity is large or small. FIGS. 13-16 are polarization curve tests of symmetric cells of zinc metal sprayed with copper or silver, from which results can be found whether at 1mAh/cm2Or at 3mAh/cm2The service life and polarization of the zinc protected under the capacity of the zinc are far better than those of original metal zinc, and the surface of the zinc protected by the metal is obviously smoother than that of the original zinc after circulation through the graphs in fig. 19-21, which shows that the metal protective layer can effectively inhibit the generation of zinc dendrites, so that the service life of the zinc cathode is prolonged. The formation of an alloy phase on the metal protective layer can be found through XRD of the battery after circulation, which shows that a part of metal and zinc form an alloy in the circulation process, and the generation of zinc dendrite can be effectively inhibited in the subsequent battery circulation. To further illustrate the advantages of the protected zinc anode in practical applications, it was combined with manganese dioxide to form a full cell (fig. 22-25), and from experimental results, it was found that the performance of the protected zinc during long cycling and rate cycling was superior to that of the original zinc. The above examples illustrate that the metal protective layer can maximize the coulombic efficiency of zinc and inhibit the generation of zinc dendrites, can effectively improve the performance of the full cell, and open up a new way for the practical application of the zinc metal cathode.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, so long as the technical principle and the inventive concept of the method for protecting a metal electrode of the present invention are met, and the present invention shall fall within the protection scope of the present invention.

Claims (7)

1. A method for protecting a metal electrode, comprising the steps of:
a. preparing a metal protective layer on the surface of an electrode material:
adopting stainless steel or metal zinc material as electrode base material, directly spraying protective layer metal on the surface of the stainless steel or metal zinc by using a physical vapor deposition method, and respectively forming metal protective layers with the thickness of 90-300 nanometers on the surfaces of the stainless steel or metal zinc;
b. preparing an electrode assembly:
cutting the metal zinc or the stainless steel for preparing the protective layer in the step a into metal zinc sheets or stainless steel sheets with the diameter not less than 10 millimeters, and using the metal zinc sheets or the stainless steel sheets as electrodes of symmetrical batteries and working electrodes in coulombic efficiency tests for standby;
c. surface alloying process of electrode assembly:
b, taking the metal zinc sheet or the stainless steel sheet cut in the step b as an electrode of a symmetrical battery or a working electrode in a coulombic efficiency test, adopting an aqueous electrolyte, wherein the electrolyte is a zinc sulfate solution with the concentration of not less than 3 mol per liter, and adding manganese sulfate into the electrolyte, wherein the concentration of the manganese sulfate is not less than 0.1 mol per liter; the electrode, the diaphragm and the electrolyte are assembled into an electrolytic device or a battery device, and when the first electrochemical reaction is carried out, an electroplating process is carried out on the surface of the electrode, so that the protective layer metal on the surface of the electrode and the electroplated zinc are subjected to an alloying process, and an alloy layer is formed on the protective layer.
2. The method for protecting a metal electrode according to claim 1, wherein: in the step a, the protective layer metal is made of any one or two metal materials of copper and silver.
3. The method for protecting a metal electrode according to claim 2, wherein: in the step a, when the protective layer metal is copper, the physical vapor deposition temperature for preparing the metal protective layer by physical vapor deposition is 1200-1400 ℃, and the thickness is not more than 300 nanometers.
4. The method for protecting a metal electrode according to claim 2, wherein: in the step a, when the protective layer metal adopts silver, the physical vapor deposition temperature for preparing the metal protective layer by physical vapor deposition is 850-1200 ℃, and the thickness is not more than 170 nanometers.
5. The method for protecting a metal electrode according to any one of claims 1 to 4, wherein: in the step a, when the physical vapor deposition is carried out to prepare the metal protective layer, the pressure of the atmosphere for carrying out the physical vapor deposition is controlled to be not more than 10-4Pa。
6. The method for protecting a metal electrode according to any one of claims 1 to 4, wherein: in the step c, the material of the diaphragm adopts glass fiber.
7. The method for protecting a metal electrode according to any one of claims 1 to 4, wherein: in said step c, the alloy layer on the surface of the electrode can also serve as a composite substrate surface inducing the uniform deposition of zinc.
CN202010278088.9A 2020-04-10 2020-04-10 Method for protecting metal electrode Pending CN111769251A (en)

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