CN112331933A - Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof - Google Patents

Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof Download PDF

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CN112331933A
CN112331933A CN202011163885.9A CN202011163885A CN112331933A CN 112331933 A CN112331933 A CN 112331933A CN 202011163885 A CN202011163885 A CN 202011163885A CN 112331933 A CN112331933 A CN 112331933A
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zinc
metal
solid electrolyte
secondary battery
electrode
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孙永明
蔡钊
欧阳涛
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Huazhong University of Science and Technology
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Huazhong University of 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/365—Zinc-halogen accumulators
    • 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
    • H01M10/38—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a preparation method of a cathode of a long-cycle-life aqueous zinc secondary battery, belonging to the technical field of zinc secondary batteries. The preparation method comprises the steps of firstly, carrying out chemical displacement reaction on zinc and metal salt to deposit a metal simple substance on the surface of the zinc metal to obtain a zinc metal surface covered solid electrolyte precursor; covering the surface of zinc metal with a solid electrolyte precursor as a negative electrode to assemble a battery; and after the solid electrolyte precursor material is subjected to in-situ electrochemical cyclic activation, in-situ generation of the solid electrolyte on the surface of the zinc metal is carried out, and the zinc secondary battery cathode material is obtained. The obtained zinc/solid electrolyte electrode has larger actual electrochemical active area and higher mechanical stability, and meanwhile, the solid electrolyte isolates zinc metal from liquid electrolyte, so that the defects of active metal corrosion, surface passivation, dendritic crystal growth and the like existing in the traditional zinc metal electrode are overcome, and the circulation stability of the electrode material is improved.

Description

Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof
Technical Field
The invention belongs to the technical field of zinc secondary batteries, and particularly relates to a preparation method of a cathode of a long-cycle-life aqueous zinc secondary battery.
Background
Renewable energy sources such as solar energy, wind energy and tidal energy are widely distributed, but the utilization and popularization of clean energy sources are severely limited by the defects of regionality, intermittency and the like, and the development of an electric energy storage technology is urgent. The metal secondary battery (such as a zinc metal battery and the like) is one of the most promising next-generation high-energy-density energy storage devices, and has good application prospects in the fields of renewable energy storage, power grid energy storage and the like. However, the problems of side reaction between the active metal zinc and the electrolyte, dendrite growth, etc. reduce the cycle life of the zinc secondary battery, and severely limit the practical application of the zinc secondary battery.
It has been reported that the electrochemical performance of zinc secondary batteries is improved by means of structural optimization of metal electrodes or design of solid electrolyte. However, the preparation method of the related electrode has the defects of long synthesis period, difficult process control or high energy consumption and the like, and is difficult to popularize in a large area. It remains a problem to design a rapid, simple and low energy-consuming synthesis method to produce zinc/solid electrolyte electrode materials on a large scale. In addition, how to design a high-performance zinc/solid electrolyte electrode by combining the optimization of the metal electrode structure and the means of solid electrolyte to improve the cycle life of the zinc secondary battery is also very challenging.
Disclosure of Invention
The invention solves the technical problems that in the prior art, the zinc metal battery has side reaction and dendritic crystal growth between active metal zinc and electrolyte, thereby reducing the cycle life of the zinc secondary battery. Aiming at the problems, the invention provides a simple and efficient chemical replacement reaction method for preparing a zinc/solid electrolyte electrode so as to prolong the cycle life of a zinc secondary battery. Firstly, zinc and metal salt are subjected to chemical displacement reaction, so that a metal simple substance is deposited on the surface of the zinc metal, and the zinc metal with the surface covered with a solid electrolyte precursor material is obtained; assembling a battery by taking zinc metal with the surface covered with the solid electrolyte precursor as a negative electrode; and after the solid electrolyte precursor material is subjected to in-situ electrochemical cyclic activation, in-situ generation of the solid electrolyte on the surface of the zinc metal is carried out, and the zinc secondary battery cathode material is obtained.
According to a first aspect of the present invention, there is provided a method for preparing a negative electrode for a zinc secondary battery by a chemical displacement reaction, comprising the steps of:
(1) putting a zinc metal foil into a metal salt solution, and performing chemical displacement reaction on zinc and the metal salt to deposit a metal simple substance on the surface of the zinc metal to obtain a zinc metal surface covered solid electrolyte precursor;
(2) assembling the zinc metal with the surface covered with the solid electrolyte precursor obtained in the step (1) as a negative electrode into a battery; the electrolyte of the battery is an inorganic salt aqueous solution containing zinc ions or an aqueous solution of hydroxide; and after the solid electrolyte precursor is subjected to in-situ electrochemical cyclic activation, the solid electrolyte is generated in situ on the surface of the zinc metal, and the zinc secondary battery cathode material is obtained.
Preferably, the metal salt in step (1) is a chloride of copper, indium, tin, cobalt, bismuth, nickel, aluminum or iron, or at least one nitrate of copper, indium, tin, cobalt, bismuth, nickel, aluminum or iron.
Preferably, the electrolyte in the step (2) is zinc sulfate aqueous solution, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; the solid electrolyte is an oxide, a hydroxide, a simple substance or an alkali sulfate.
Preferably, the oxide is bismuth oxide or aluminum oxide; the hydroxide is tin hydroxide or ferric hydroxide; the simple substance is metal copper, metal cobalt or metal nickel; the basic sulfate is basic indium sulfate.
Preferably, the current density of the electrochemical cyclic activation is 0.1-20mA/cm2The specific area capacity is 0.1-20mAh/cm2。
According to another aspect of the present invention, there is provided a zinc secondary battery negative electrode prepared by any one of the methods.
Preferably, the solid electrolyte of the cathode of the zinc secondary battery uniformly covers the surface of the zinc metal, and the thickness of the solid electrolyte is 0.1-20.0 μm.
Preferably, the solid electrolyte is interdigitated with the zinc metal, and the depth of the solid electrolyte interpenetrated into the zinc metal is 0.5 to 50.0 μm.
According to another aspect of the present invention there is provided a zinc secondary battery comprising a zinc secondary battery negative electrode as claimed in any one of claims 6 to 8.
Preferably, the zinc secondary battery is a neutral or alkaline zinc battery.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the invention provides a chemical displacement reaction preparation method of a zinc/solid electrolyte electrode, which comprises the steps of carrying out chemical displacement reaction on a polycrystalline zinc metal foil and a specific metal precursor, depositing the corresponding metal precursor on the surface of active metal and a crystal boundary, and converting the corresponding precursor into a solid electrolyte in situ in an electrochemical circulation process to form the zinc/solid electrolyte electrode material. The solid electrolyte with a certain thickness uniformly covers the surface of the metal zinc to isolate the zinc metal from the liquid electrolyte, so that the occurrence of side reaction of the active metal is avoided, and the coulomb efficiency of the electrode is improved. Meanwhile, the solid electrolyte can be mutually interpenetrated with active zinc metal to form a three-dimensional electrode structure, so that a rich contact interface is formed, the optimization of a diffusion passage of metal ions is facilitated, the growth of metal dendrites is inhibited, and the cycle life of the zinc secondary battery is finally prolonged.
(2) The invention utilizes a chemical displacement reaction method to deposit metal precursors on the surface and the grain boundary of zinc metal. Controlling the chemical replacement rate of the specific metal salt and the zinc metal to be high leads to covering the metal precursor on the surface of the zinc metal, and controlling the chemical replacement rate of the metal salt and the zinc metal to be low leads to diffusing the metal precursor at the crystal boundary of the zinc metal to form a three-dimensional interpenetrating metal precursor structure. The corresponding precursor is converted into a protective layer structure (solid electrolyte) with high ionic conductivity and good stability in situ in the subsequent electrochemical activation process. The obtained zinc/solid electrolyte electrode has larger actual electrochemical active area and higher mechanical stability, and meanwhile, the solid electrolyte isolates zinc metal from liquid electrolyte, so that the defects of active metal corrosion, surface passivation, dendritic crystal growth and the like existing in the traditional zinc metal electrode are overcome, and the circulation stability of the electrode material is improved.
(3) The thickness of the zinc/solid electrolyte electrode surface evenly covered with the solid electrolyte prepared by the invention is 0.1-20 μm. The depth of the solid electrolyte which can be penetrated into the metal is 0.5-50 μm, and a large number of three-dimensional contact interfaces are contained between the active metal zinc and the solid electrolyte.
(4) The solid electrolyte material prepared by the method is obtained by in-situ electrochemical activation of metal (namely a solid electrolyte precursor) deposited by a displacement reaction in an aqueous electrolyte. The metal with negative electrode potential is oxidized during electrochemical cycling to form thermodynamically stable oxide, hydroxide or oxysulfate solid electrolyte. The metal with positive electrode potential remains stable during electrochemical cycling to form a metallic solid electrolyte. The migration of zinc ions in an electrode material bulk phase in the electrochemical circulation process can promote the nanocrystallization of a metal solid electrolyte precursor, the finally formed solid electrolyte material is composed of compact amorphous nanoparticles, the average particle size of the particles is only 5-100nm, and metal ions can be conducted at the interface of the nanoparticles.
(5) The side reaction of the zinc/solid electrolyte electrode prepared by the method is effectively inhibited, and the side reaction rate is only 5-50% of that of a pure zinc electrode.
(6) The cycle life of the zinc/solid electrolyte electrode prepared by the invention can reach 2-15 times of that of a pure zinc electrode, and the zinc/solid electrolyte electrode can realize large current and large surface capacity (the maximum can reach 20 mA/cm)2And 20mAh/cm2) And (4) stable circulation under the condition.
(7) The chemical displacement reaction preparation method of the zinc/solid electrolyte electrode is simple and easy for industrial popularization.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a zinc/basic indium sulfate electrode obtained in example 1 according to the present invention.
FIG. 2 is an electron probe X-ray microanalysis of a cross-section of a zinc/indium oxysulfate basic electrode obtained in example 1 according to the invention.
Fig. 3 is a high-resolution transmission electron microscope image of a basic indium sulfate solid electrolyte obtained in example 1 according to the present invention.
FIG. 4 is an infrared spectrum of a zinc/basic indium sulfate electrode obtained in example 1 according to the present invention.
FIG. 5 is a comparison of the hydrogen evolution side reaction rates of the zinc/basic indium sulfate electrode obtained in example 1 according to the invention with a pure zinc electrode.
Fig. 6 is an electrochemical impedance spectrum of a zinc/basic indium sulfate electrode obtained in example 1 according to the present invention.
FIG. 7 shows a symmetrical cell at 1mA/cm assembled with zinc/basic indium sulfate electrodes obtained in example 1 according to the present invention2And 0.5mAh/cm2Performance plots under the conditions.
FIG. 8 shows a 20mA/cm symmetrical cell assembled with Zn/basic indium sulfate electrodes obtained in example 1 according to the present invention2And 20mAh/cm2Performance plots under the conditions.
FIG. 9 is an electron probe X-ray microanalysis of a cross-section of a zinc/tin hydroxide electrode obtained in example 2 according to the present invention.
FIG. 10 shows a symmetrical cell at 0.1mA/cm with zinc/tin hydroxide electrode assembly obtained in example 2 according to the invention2And 0.1mAh/cm2Performance plots under the conditions.
FIG. 11 is a scanning electron microscope image and elemental distribution map of a cross section of a zinc/alumina electrode obtained in example 3 according to the present invention.
FIG. 12 shows a symmetrical cell at 5mA/cm with zinc/alumina electrodes assembled as obtained in example 3 according to the invention2And 2mAh/cm2Performance plots under the conditions.
FIG. 13 is a scanning electron microscope image and elemental distribution map of a cross section of a zinc/copper electrode obtained in example 4 according to the present invention.
FIG. 14 shows a zinc/copper electrode assembly of a symmetrical cell at 1mA/cm obtained in example 4 according to the invention2And 1mAh/cm2Performance plots under the conditions.
FIG. 15 shows a symmetrical cell at 1mA/cm of an assembled Zn/in-Sn composite hydroxide electrode obtained in example 5 according to the present invention2And 0.5mAh/cm2Performance plots under the conditions.
FIG. 16 shows a symmetrical cell at 1mA/cm with an assembled Zn/Ni-Co-Cu electrode obtained in example 6 according to the present invention2And 0.5mAh/cm2Performance plots under the conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
A method for preparing a long-cycle-life zinc secondary battery cathode material by chemical replacement reaction comprises the following steps:
(1) taking a zinc metal foil, and washing the zinc metal foil in dilute hydrochloric acid and deionized water for later use;
(2) putting the zinc foil in the step (1) into a metal salt solution, stirring and reacting for 1-10 minutes under the conditions of normal temperature and normal pressure, carrying out chemical displacement reaction on zinc and the metal salt, depositing a metal simple substance on the surface and the crystal boundary of zinc metal to obtain a zinc/solid electrolyte precursor material, and washing the zinc/solid electrolyte precursor material with absolute ethyl alcohol or deionized water for later use;
(3) and (3) taking the zinc/solid electrolyte precursor material in the step (2) as a negative electrode assembly battery, and carrying out electrochemical cycle activation to obtain the long-cycle-life zinc secondary battery negative electrode material.
In some embodiments, the metallic zinc foil is polycrystalline, rich in grain boundaries.
In some embodiments, the specific metal salt is one or more of a chloride or nitrate of a metal such as copper, indium, tin, cobalt, bismuth, nickel, aluminum, iron, and the like.
In some embodiments, the solvent of the specific metal salt solution in step (2) is deionized water, ethanol, ethylene glycol, or a mixed solvent thereof.
In some embodiments, the electrochemically cycled activation current density in step (3) is from 0.1 to 20mA/cm2Area ratio ofThe capacity is 0.1-20mAh/cm2。
In some embodiments, the solid electrolyte uniformly covers the metal surface and has a thickness of 0.1-20.0 μm; in addition, the solid electrolyte may be interdigitated with the metal, and the depth of the solid electrolyte penetrating into the metal is 0.5 to 50.0 μm.
The active metal zinc of the zinc/solid electrolyte secondary battery electrode prepared by the invention is tightly combined with the solid electrolyte to form an electrode material with a stable mechanical structure, and the electrode material has long cycle life.
Example 1
Preparing a zinc/basic indium sulfate electrode material by the following chemical replacement reaction method:
A. preparing reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, indium chloride ethanol solution with the concentration of 0.1mol/L and zinc sulfate aqueous solution with the concentration of 3 mol/L.
B. And B, pretreating the commercial polycrystalline metal zinc foil, ultrasonically cleaning the commercial polycrystalline metal zinc foil in 0.1mol/L dilute hydrochloric acid and deionized water for 2 minutes, then soaking the pretreated zinc foil into the 0.1mol/L indium chloride ethanol solution obtained in the step A, stirring and reacting for 10 minutes at normal temperature and normal pressure, then taking out, washing and drying to obtain the zinc/indium precursor material.
C. And D, assembling the zinc/indium precursor material obtained in the step B into a symmetrical battery, and taking the 3mol/L zinc sulfate aqueous solution obtained in the step A as an electrolyte and the glass fiber as a diaphragm. At 20mA/cm2And 20mAh/cm2And electrochemically circulating for 5 circles under the condition to obtain the zinc/basic indium sulfate electrode material.
The test results were as follows:
FIG. 1 is a scanning electron micrograph of the surface of the zinc/basic indium sulfate electrode obtained in example 1. It can be seen from the figure that the prepared electrode has a flat and dense surface.
FIG. 2 is an electron probe X-ray microanalysis of a cross-section of the zinc/indium oxysulfate basic electrode obtained in example 1. It can be seen from the figure that the zinc metal and the basic indium sulfate solid electrolyte are interpenetrated, the thickness of the surface solid electrolyte is 2.3 μm, and the interpenetration depth of the solid electrolyte is 40 μm, so as to form a three-dimensional electrode structure.
Fig. 3 is a high-resolution transmission electron microscope image of basic indium sulfate obtained in example 1. It can be seen from the figure that the basic indium sulfate solid electrolyte is a dense material composed of amorphous basic indium sulfate nanoparticles of about 7 nm.
FIG. 4 is an infrared spectrum of a zinc/basic indium sulfate electrode obtained in example 1. The characteristic infrared absorption peaks of hydroxide and sulfate of the basic indium sulfate material can be seen from the figure.
FIG. 5 is a comparison of the hydrogen evolution side reaction rates of the zinc/indium oxysulfate basic electrode obtained in example 1 with a pure zinc electrode. Hydrogen evolution side reaction rate (0.002 cm) of zinc/basic indium sulfate solid electrolyte electrode in electrochemical cycle process3mAh) is a pure zinc electrode only (0.032 cm)36.25% of mAh).
FIG. 6 is an electrochemical impedance spectrum of the zinc/basic indium sulfate electrode obtained in example 1. The electrochemical impedance of the zinc/basic indium sulfate solid state electrolyte electrode (36 Ω) is only about one-fourth of that of a pure zinc electrode (154 Ω).
FIG. 7 shows the current density at 1mA/cm for a symmetrical cell assembled with Zn/basic indium sulfate electrode obtained in example 12And 0.5mAh/cm2Performance plots under the conditions. The prepared zinc/basic indium sulfate electrode can stably circulate for more than 700 hours, the average overpotential of the zinc/basic indium sulfate electrode is only 8mV, the pure zinc electrode can continuously circulate for only 80 hours, and the average overpotential is more than 20 mV.
FIG. 8 shows the current density at 20mA/cm for a symmetrical cell assembled with Zn/basic indium sulfate electrode obtained in example 12And 20mAh/cm2Performance plots under the conditions. The prepared zinc/basic indium sulfate electrode can stably circulate for more than 80 hours, the average overpotential of the zinc/basic indium sulfate electrode is only 10mV, the pure zinc electrode cannot stably circulate under the same condition, and the average overpotential of the pure zinc electrode is more than 150 mV.
Example 2
Preparing a zinc/tin hydroxide electrode material by the following chemical displacement reaction method:
A. preparing reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, tin chloride ethanol solution with the concentration of 0.1mol/L and potassium hydroxide aqueous solution with the concentration of 6 mol/L.
B. And (2) pretreating the commercial polycrystalline metal zinc foil, ultrasonically cleaning the commercial polycrystalline metal zinc foil in 0.1mol/L dilute hydrochloric acid and deionized water for 2 minutes in sequence, then soaking the pretreated zinc foil into the 0.1mol/L tin chloride ethanol solution obtained in the step A, stirring and reacting for 10 minutes at normal temperature and normal pressure, then taking out, washing and drying to obtain the zinc/tin precursor material.
C. And D, assembling the zinc/tin precursor material obtained in the step B into a symmetrical battery, and taking the 6mol/L potassium hydroxide aqueous solution obtained in the step A as an electrolyte and the glass fiber as a diaphragm. At 0.1mA/cm2And 0.1mAh/cm2And electrochemically circulating for 5 circles under the condition to obtain the zinc/tin hydroxide electrode material.
The test results were as follows:
FIG. 9 is an electron probe X-ray microanalysis of a cross-section of a zinc/tin hydroxide electrode obtained in accordance with a preferred embodiment 2 of the present invention. It can be seen from the figure that the zinc metal and the tin hydroxide solid electrolyte are interpenetrated, the thickness of the surface solid electrolyte is 0.2 μm, the interpenetration depth of the solid electrolyte is 0.5-40 μm (the average interpenetration depth is 22 μm), and a three-dimensional electrode structure is formed.
FIG. 10 shows the zinc/tin hydroxide electrode assembly of a symmetrical cell at 0.1mA/cm obtained in example 22And 0.1mAh/cm2Performance plots under the conditions. The prepared zinc/tin hydroxide electrode can stably circulate for more than 200 hours, and the average over-potential is 12 mV.
Example 3
Preparing a zinc/aluminum oxide electrode material by the following chemical displacement reaction method:
A. preparing reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, aluminum chloride aqueous solution with the concentration of 0.05mol/L and zinc sulfate aqueous solution with the concentration of 3 mol/L.
B. And (2) pretreating the commercial polycrystalline metal zinc foil, ultrasonically cleaning the commercial polycrystalline metal zinc foil in 0.1mol/L dilute hydrochloric acid and deionized water for 2 minutes, then soaking the pretreated zinc foil into the 0.05mol/L aluminum chloride aqueous solution obtained in the step A, stirring and reacting for 10 minutes at normal temperature and normal pressure, then taking out, washing and drying to obtain the zinc/aluminum precursor material.
C. B, assembling the zinc/aluminum precursor material obtained in the step B into a symmetrical battery, and performing the step A3mol/L zinc sulfate aqueous solution is used as electrolyte, and glass fiber is used as a diaphragm. At 5mA/cm2And 2mAh/cm2And performing electrochemical circulation for 20 circles under the condition to obtain the zinc/aluminum oxide electrode material.
The test results were as follows:
FIG. 11 is a scanning electron microscope image and elemental distribution map of a cross section of a zinc/alumina electrode obtained in preferred embodiment 3 according to the present invention. The thickness of the prepared tin hydroxide solid electrolyte on the surface of the zinc/aluminum oxide electrode is 7.2 mu m.
FIG. 12 shows the zinc/alumina electrode assembly of a symmetrical cell at 5mA/cm obtained in example 32And 2mAh/cm2Performance plots under the conditions. The prepared zinc/aluminum oxide electrode can stably circulate for more than 300 hours, and the average over-potential is 18 mV.
Example 4
Preparing a zinc/copper electrode material by the following chemical displacement reaction method:
A. preparing reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, copper chloride glycol solution with the concentration of 0.01mol/L and zinc sulfate aqueous solution with the concentration of 3 mol/L.
B. And (2) pretreating the commercial polycrystalline metal zinc foil, carrying out ultrasonic cleaning in 0.1mol/L dilute hydrochloric acid and deionized water for 2 minutes in sequence, then immersing the pretreated zinc foil into the 0.01mol/L copper chloride glycol solution obtained in the step A, carrying out stirring reaction for 3 minutes at normal temperature and normal pressure, then taking out, washing and drying to obtain the zinc/copper precursor material.
C. And D, assembling the zinc/copper precursor material obtained in the step B into a symmetrical battery, and taking the 3mol/L zinc sulfate aqueous solution obtained in the step A as an electrolyte and the glass fiber as a diaphragm. At 1mA/cm2And 1mAh/cm2And performing electrochemical circulation for 10 circles under the condition to obtain the zinc/copper electrode material.
The test results were as follows:
FIG. 13 is a scanning electron microscope image and elemental distribution map of a cross section of a zinc/copper electrode obtained in preferred embodiment 4 according to the present invention. The thickness of the prepared copper solid electrolyte on the surface of the zinc/copper electrode is 20.5 mu m.
FIG. 14 shows a symmetrical cell with zinc/copper electrode assembly obtained in example 41mA/cm2And 1mAh/cm2Performance plots under the conditions. The prepared zinc/copper electrode can stably circulate for more than 500 hours, and the average over-potential is 22 mV.
Example 5
Preparing a zinc/indium tin composite hydroxide electrode material by the following chemical displacement reaction method:
A. preparing reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, indium chloride ethanol solution with the concentration of 0.1mol/L, stannic chloride ethanol solution with the concentration of 0.1mol/L and zinc sulfate aqueous solution with the concentration of 3 mol/L.
B. And (2) pretreating a commercial polycrystalline metal zinc foil, ultrasonically cleaning the commercial polycrystalline metal zinc foil in 0.1mol/L dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 minutes in sequence, then immersing the pretreated zinc foil into a mixed solution (volume ratio is 1:1) containing 0.1mol/L indium chloride ethanol solution and 0.1mol/L tin chloride ethanol solution in the step A, stirring and reacting for 10 minutes at normal temperature and normal pressure, taking out, washing and drying to obtain the zinc/indium tin precursor material.
C. And D, assembling the zinc/indium tin precursor material obtained in the step B into a symmetrical battery, and taking the 3mol/L zinc sulfate aqueous solution obtained in the step A as an electrolyte and the glass fiber as a diaphragm. At 1mA/cm2And 0.5mAh/cm2And electrochemically circulating for 20 circles under the condition to obtain the zinc/indium-tin composite hydroxide electrode material.
The test results were as follows:
FIG. 15 shows the voltage at 1mA/cm of a symmetrical cell assembled by the Zn/in-Sn composite hydroxide electrode obtained in example 52And 0.5mAh/cm2Performance plots under the conditions. The prepared zinc/indium-tin composite hydroxide electrode can stably circulate for more than 400 hours, and the average over-potential is 11 mV.
Example 6
Preparing a zinc/nickel-cobalt-copper electrode material by the following chemical displacement reaction method:
A. preparing a reaction solution, dilute hydrochloric acid with the concentration of 0.1mol/L, a nickel nitrate aqueous solution with the concentration of 0.05mol/L, a cobalt chloride ethanol solution with the concentration of 0.05mol/L, a copper chloride glycol solution with the concentration of 0.02mol/L and a zinc sulfate aqueous solution with the concentration of 3 mol/L.
B. Pretreating a commercial polycrystalline metal zinc foil, ultrasonically cleaning the commercial polycrystalline metal zinc foil in 0.1mol/L dilute hydrochloric acid, deionized water and absolute ethyl alcohol for 2 minutes in sequence, then immersing the pretreated zinc foil into a mixed solution (volume ratio is 1:1:1) containing 0.05mol/L nickel nitrate aqueous solution, 0.05mol/L cobalt chloride ethanol solution and 0.02mol/L copper chloride glycol solution in the step A, stirring and reacting for 5 minutes at normal temperature and normal pressure, taking out, washing and drying to obtain the zinc/nickel-cobalt-copper precursor material.
C. And D, assembling the zinc/nickel-cobalt-copper precursor material obtained in the step B into a symmetrical battery, and taking the 3mol/L zinc sulfate aqueous solution obtained in the step A as an electrolyte and the glass fiber as a diaphragm. At 1mA/cm2And 0.5mAh/cm2And electrochemically circulating for 5 circles under the condition to obtain the zinc/nickel-cobalt-copper electrode material.
The test results were as follows:
FIG. 16 shows the current cell density at 1mA/cm for a symmetrical cell assembled with Zn/Ni-Co-Cu electrodes obtained in example 62And 0.5mAh/cm2Performance plots under the conditions. The prepared zinc/nickel-cobalt-copper electrode can stably circulate for more than 1000 hours, and the average over potential is 20 mV.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A method for preparing a zinc secondary battery cathode by chemical replacement reaction is characterized by comprising the following steps:
(1) putting a zinc metal foil into a metal salt solution, and performing chemical displacement reaction on zinc and the metal salt to deposit a metal simple substance on the surface of the zinc metal to obtain a zinc metal surface covered solid electrolyte precursor;
(2) assembling the zinc metal with the surface covered with the solid electrolyte precursor obtained in the step (1) as a negative electrode into a battery; the electrolyte of the battery is an inorganic salt aqueous solution containing zinc ions or an aqueous solution of hydroxide; and after the solid electrolyte precursor is subjected to in-situ electrochemical cyclic activation, the solid electrolyte is generated in situ on the surface of the zinc metal, and the zinc secondary battery cathode material is obtained.
2. The method for preparing a negative electrode of a zinc secondary battery by chemical displacement reaction according to claim 1, wherein the metal salt in the step (1) is a chloride of copper, indium, tin, cobalt, bismuth, nickel, aluminum or iron, or at least one nitrate of copper, indium, tin, cobalt, bismuth, nickel, aluminum or iron.
3. The method for preparing a negative electrode for a zinc secondary battery by chemical displacement reaction according to claim 1, wherein the electrolyte in the step (2) is an aqueous solution of zinc sulfate, sodium hydroxide or potassium hydroxide; the solid electrolyte is an oxide, a hydroxide, a simple substance or an alkali sulfate.
4. The method for preparing a negative electrode for a zinc secondary battery by chemical displacement reaction according to claim 3, wherein the oxide is bismuth oxide or aluminum oxide; the hydroxide is tin hydroxide or ferric hydroxide; the simple substance is metal copper, metal cobalt or metal nickel; the basic sulfate is basic indium sulfate.
5. The method for preparing a negative electrode for a zinc secondary battery by chemical displacement reaction according to claim 1, wherein the current density of electrochemical cyclic activation is 0.1-20mA/cm2The specific area capacity is 0.1-20mAh/cm2。
6. A zinc secondary battery negative electrode prepared by the method of any one of claims 1 to 5.
7. The negative electrode of a zinc secondary battery according to claim 6, wherein the solid electrolyte of the negative electrode of a zinc secondary battery uniformly covers the surface of the zinc metal, and the thickness of the solid electrolyte is 0.1 to 20.0 μm.
8. The zinc secondary battery negative electrode according to claim 7, wherein the solid electrolyte is interdigitated with the zinc metal and the depth of the solid electrolyte interpenetrated into the zinc metal is 0.5 to 50.0 μm.
9. A zinc secondary battery comprising the negative electrode for a zinc secondary battery according to any one of claims 6 to 8.
10. The zinc secondary battery according to claim 9, wherein the zinc secondary battery is a neutral or alkaline zinc battery.
CN202011163885.9A 2020-10-27 2020-10-27 Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof Pending CN112331933A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005435A (en) * 2021-02-09 2021-06-22 浙江工业大学 Zinc metal protective layer material and preparation method and application thereof
CN113363427A (en) * 2021-06-07 2021-09-07 中南大学 Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
CN115020706A (en) * 2022-05-30 2022-09-06 西南科技大学 Water-based zinc ion battery, rolled hectorite @ zinc negative electrode material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103675068A (en) * 2013-03-28 2014-03-26 浙江大学 Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof
CN106887581A (en) * 2015-12-16 2017-06-23 中国科学院大连化学物理研究所 A kind of zinc electrode material and its preparation and application
CN111312984A (en) * 2020-02-25 2020-06-19 天津大学 Preparation method of aqueous corrosion-resistant dendritic-free metal negative electrode
CN111769251A (en) * 2020-04-10 2020-10-13 上海大学 Method for protecting metal electrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103675068A (en) * 2013-03-28 2014-03-26 浙江大学 Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof
CN106887581A (en) * 2015-12-16 2017-06-23 中国科学院大连化学物理研究所 A kind of zinc electrode material and its preparation and application
CN111312984A (en) * 2020-02-25 2020-06-19 天津大学 Preparation method of aqueous corrosion-resistant dendritic-free metal negative electrode
CN111769251A (en) * 2020-04-10 2020-10-13 上海大学 Method for protecting metal electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113005435A (en) * 2021-02-09 2021-06-22 浙江工业大学 Zinc metal protective layer material and preparation method and application thereof
CN113363427A (en) * 2021-06-07 2021-09-07 中南大学 Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
CN115020706A (en) * 2022-05-30 2022-09-06 西南科技大学 Water-based zinc ion battery, rolled hectorite @ zinc negative electrode material and preparation method thereof
CN115020706B (en) * 2022-05-30 2023-06-09 西南科技大学 Water-based zinc ion battery, rolled hectorite@zinc anode material and preparation method thereof

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