CN114094114A - Sodium battery current collector and preparation method and application thereof - Google Patents

Sodium battery current collector and preparation method and application thereof Download PDF

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CN114094114A
CN114094114A CN202111395963.2A CN202111395963A CN114094114A CN 114094114 A CN114094114 A CN 114094114A CN 202111395963 A CN202111395963 A CN 202111395963A CN 114094114 A CN114094114 A CN 114094114A
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sodium
aluminum
metal
current collector
gallium
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冯金奎
魏传亮
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Shandong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention relates to a sodium battery current collector and a preparation method and application thereof, in particular to a method for improving the wettability of the current collector to metal sodium, reducing the nucleation overpotential of sodium and inhibiting the growth of sodium dendrite by modifying the surface of an aluminum-based current collector by using room-temperature gallium-based liquid metal. The method comprises the following steps: and (3) coating a layer of room-temperature gallium-based liquid metal on the surface of the metal aluminum, and then carrying out liquid metal diffusion reaction to obtain the gallium-based aluminum alloy. According to the invention, the gallium-based liquid metal is coated on the surface of the metal aluminum, and a sodium-philic aluminum-gallium alloy layer is spontaneously formed on the surface of the metal aluminum, so that the nucleation overpotential of the metal sodium is reduced, the growth of sodium dendrite is inhibited, and the cycle stability, the service life and the coulombic efficiency of the sodium battery are improved.

Description

Sodium battery current collector and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium-ion batteries, and particularly relates to a sodium battery current collector and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Due to the widespread storage of sodium resources worldwide, sodium ion batteries are considered to be one of the most promising new battery systems. The metallic sodium is an excellent sodium ion battery cathode material and has the advantages of high theoretical specific capacity (1165mAh/g), low electrochemical potential (-2.37V), good conductivity and the like. However, the development and application of metallic sodium cathodes have been limited by problems such as growth of sodium dendrites, unstable interfaces, volume changes of the electrodes, and the like. Some strategies for modifying metallic sodium anodes have been reported, however, the inventors have found that: most strategies have the problems of complex method, high toxicity, high cost and the like.
Disclosure of Invention
Aiming at the problems, the invention provides a sodium battery current collector for inhibiting the growth of sodium dendrites, and a preparation method and application thereof. The preparation method is a method for preparing the high-performance metallic sodium negative current collector with low cost, simple synthesis and no pollution, synthesizes the metallic sodium negative material with long service life and high stability, and applies the metallic sodium negative material to the high-energy-density sodium metal battery, thereby having great significance for greatly promoting the development of novel energy storage equipment and the development of new energy industry.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing a sodium battery current collector, comprising: and coating a layer of room-temperature gallium-based liquid metal on the surface of the metal aluminum, standing for diffusion reaction, and forming an aluminum-gallium alloy layer on the surface of the metal aluminum to obtain the current collector.
Because the gaps among the aluminum atoms in the metal aluminum are large, the gallium-based liquid metal can be easily diffused into the gaps, and an aluminum-gallium connected interface is further formed. One of the characteristics of the method of the invention is as follows: the gallium-based liquid metal with high conductivity, low melting point, good fluidity, environmental friendliness and sodium affinity at room temperature is smeared on the surface of metal aluminum to form a sodium affinity interface. The interface layer can reduce the nucleation overpotential of sodium and inhibit the growth of sodium dendrites.
The synthesis method adopted by the invention is simple, green and environment-friendly, has low cost and has good large-scale production advantages.
In a second aspect of the present invention, there is provided a sodium battery current collector prepared by the above preparation method, which includes: metal aluminum and an aluminum-gallium alloy layer attached to the surface of the metal aluminum.
In a third aspect of the present invention, a highly stable metallic sodium electrode is provided, wherein a certain amount of metallic sodium is deposited on the current collector by using an electrodeposition method to form the metallic sodium electrode.
In a fourth aspect of the invention, the application of the metal sodium electrode in the manufacture of sodium batteries, smart grids, electronic products, electric automobiles and mobile energy storage devices is provided.
The invention effectively improves the cycling stability of the metal sodium cathode, inhibits the growth of sodium dendrite, and is expected to be widely applied to an energy storage device, thereby promoting the development of new energy industry and social progress.
The invention has the beneficial effects that:
(1) the invention adopts environment-friendly room-temperature gallium-based liquid metal as the surface modifier, and has no problem of environmental pollution.
(2) The current collector synthesis method adopted by the invention has the advantages of simplicity, easiness in implementation, low cost, easiness in large-scale production and the like.
(3) The method provided by the invention utilizes the principle that the room-temperature gallium-based liquid metal can be rapidly diffused on the surface of the metal aluminum to form the aluminum-gallium interface layer. Because the metal gallium has certain sodium affinity, the wettability of the modified current collector to the metal sodium is improved, the nucleation overpotential of the metal sodium can be reduced, the growth of sodium dendrites is further inhibited, the cycle stability and the safety of the metal sodium cathode are improved, and the service life of the metal sodium cathode is prolonged.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic flow chart of the process for preparing a current collector of a sodium battery capable of inhibiting the growth of sodium dendrites according to examples 1-9 of the present invention.
FIG. 2 is a scanning electron micrograph of an aluminum foil in a comparative example of the present invention.
Fig. 3 is a scanning electron microscope image of a GaInSnZn liquid metal modified aluminum foil in example 1 of the present invention.
Fig. 4 is a graph of nucleation overpotentials for sodium metal on aluminum foil current collectors and GaInSnZn liquid metal modified aluminum foil current collectors in comparative example and example 1 of the present invention.
FIG. 5 shows the current collector of aluminum foil at 0.2mA/cm in comparative example of the present invention2Current density deposition of 2mAh/cm2Scanning electron micrographs of sodium metal.
FIG. 6 shows the current collector of the aluminum foil modified with GaInSnZn liquid metal at 0.2mA/cm in example 1 of the present invention2Current density deposition of 2mAh/cm2Scanning electron micrographs of sodium metal.
Fig. 7 is a graph of coulombic efficiencies for aluminum foil current collectors and GaInSnZn liquid metal modified aluminum foil current collectors in comparative examples and example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As previously mentioned, the uncontrolled growth of sodium dendrites not only creates a safety hazard, but also increases the side reactions between the metallic sodium cathode and the electrolyte, severely reducing the cycle stability and life of the sodium metal cathode. Most of the existing modification strategies have the problems of complex method, high toxicity, high cost and the like.
Therefore, the invention provides a surface modification strategy which is green, environment-friendly, simple and easy to operate, namely, the invention utilizes the principle that the room-temperature gallium-based liquid metal can be rapidly diffused on the surface of the metal aluminum to form an aluminum-gallium interface alloy layer, and the room-temperature gallium-based liquid metal (the melting point is 0-30 ℃) is coated on the surface of the metal aluminum to prepare the sodium battery current collector capable of inhibiting the growth of sodium dendrites.
This technical solution will now be further explained.
A preparation method of a sodium battery current collector comprises the following steps: and coating a layer of room-temperature gallium-based liquid metal on the surface of the metal aluminum, standing for diffusion reaction, and forming an aluminum-gallium alloy layer on the surface of the metal aluminum to obtain the current collector.
The sodium battery current collector prepared by the preparation method comprises the following steps: metal aluminum and an aluminum-gallium alloy layer attached to the surface of the metal aluminum.
A high-stability metallic sodium electrode is formed by depositing a certain amount of metallic sodium on a current collector by using an electrodeposition method.
The metal sodium electrode is applied to the manufacture of sodium batteries, smart power grids, electronic products, electric automobiles and mobile energy storage equipment.
In some exemplary embodiments, the metallic aluminum includes, but is not limited to: any one of aluminum sheet, aluminum tape, aluminum wire, aluminum powder, aluminum block, aluminum wire, foamed aluminum, aluminum mesh, and the like. Further, the aluminum sheet is an aluminum foil.
In some exemplary embodiments, the room temperature gallium-based liquid metal includes any one of gallium, gallium-zinc alloy, gallium-indium-tin-zinc alloy, and the like.
In some exemplary embodiments, the gallium-based room temperature liquid metal is applied to the aluminum metal in an amount of 0.05 to 10mg/cm2。
In some typical embodiments, the standing reaction time is 0.1 to 10 hours and the reaction temperature is 5 ℃ to 80 ℃.
In some exemplary embodiments, the battery composition at the time of electrodeposition includes a current collector, a metal sodium sheet, an electrolyte, a separator, and the like, and is assembled under an inert atmosphere.
In some exemplary embodiments, the electrolyte is an ether, an ester, a nitrile, or the like.
In some exemplary embodiments, the inert atmosphere is argon, nitrogen, a hydrogen argon mixture, helium, a vacuum atmosphere, or the like, having an oxygen content of less than 0.1ppm and a moisture content of less than 0.1 ppm.
In some exemplary embodiments, the deposition current is 0.05-20mA/cm 2.
In some exemplary embodiments, the deposition capacity is 0.5 to 50mAh/cm 2.
In some exemplary embodiments, the positive electrode of the sodium battery is sulfur, sodium vanadium phosphate, sodium iron phosphate, or the like.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
Preparation of a sodium battery current collector for inhibiting sodium dendrite growth, comprising the following steps (figure 1):
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like. The scanning electron micrograph thereof is shown in FIG. 2.
(2) And (3) rapidly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reacting for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2. The scanning electron micrograph thereof is shown in FIG. 3.
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The scanning electron micrograph is shown in FIG. 5. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 2
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) And (3) quickly coating a layer of GaInSn liquid metal on the surface of the cleaned aluminum foil by using a small hairbrush, and standing for reacting for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metallic sodium of (2). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 3
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like. The scanning electron micrograph is shown in FIG. 2.
(2) And (3) rapidly coating a layer of GaZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reacting for 1 hour. The loading amount of gallium on the magnesium foil is 0.2mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by taking an aluminum foil modified by GaZn liquid metal as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of2mAh/cm of deposition on the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 4
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps
(1) And wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) Quickly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reaction for 1 hour. The loading capacity of gallium on the aluminum foil is 0.5mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 5
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) Quickly cleaned by a small brushAnd coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil, and standing for reaction for 1 h. The loading capacity of gallium on the aluminum foil is 1mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the metal sodium electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 6
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) Quickly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reaction for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using the ratio of 0.5mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 7
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) And (3) rapidly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reacting for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2。
(3) Assembling a CR2032 type button cell in an inert atmosphere by taking an aluminum foil modified by GaInSnZn liquid metal as a current collector and a metal sodium sheet as a counter electrode, and using the aluminum foil and the metal sodium sheet as 10mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Example 8
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) And (3) rapidly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reacting for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive shell (stainless steel),Negative electrode casing (stainless steel), gasket (stainless steel), current collector, sodium piece, electrolyte and diaphragm (glass fibre).
(4) And (4) disassembling the battery with the sodium metal deposited in the step (3) in an inert atmosphere to obtain a sodium metal electrode, matching the sodium metal electrode with a sulfur positive electrode to form a CR2032 button cell, and evaluating the performance of the battery.
Example 9
The preparation method of the sodium battery current collector for inhibiting the growth of sodium dendrites comprises the following steps:
(1) and wiping the surface of the aluminum foil by absolute ethyl alcohol to remove impurities such as oil stains, dust and the like.
(2) And (3) rapidly coating a layer of GaInSnZn liquid metal on the surface of the cleaned aluminum foil by using a small brush, and standing for reacting for 1 hour. The loading capacity of gallium on the aluminum foil is 0.2mg/cm2。
(3) Assembling a CR2032 button cell in an inert atmosphere by using a GaInSnZn liquid metal modified aluminum foil as a current collector and a metal sodium sheet as a counter electrode, and using 0.2mA/cm2Current density of 2mAh/cm onto the current collector2The metal sodium of (1). The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(4) And (4) disassembling the battery with the metal sodium deposited in the step (3) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with an iron sodium phosphate positive electrode to form a CR2032 button battery, and evaluating the performance of the battery.
Comparative example
The implementation of the comparative example mainly comprises the following steps:
(1) and wiping the surface of the aluminum foil by using absolute ethyl alcohol to remove impurities such as oil stains, dust and the like. The scanning electron micrograph is shown in FIG. 2.
(2) Assembling the CR2032 button cell in an inert atmosphere by using the aluminum foil in the step (1) as a current collector and a metal sodium sheet as a counter electrode, and using the aluminum foil as a current collector and the metal sodium sheet as a counter electrode, wherein the current collector and the metal sodium sheet are arranged at a ratio of 0.2mA/cm2Current density of 2mAh/cm onto the current collector2Gold (II) ofIt belongs to sodium. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The scanning electron micrograph is shown in FIG. 4. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a sodium sheet, electrolyte and a diaphragm (glass fiber).
(3) And (3) disassembling the battery with the metal sodium deposited in the step (2) in an inert atmosphere to obtain a metal sodium electrode, matching the electrode with a vanadium sodium phosphate positive electrode to form a CR2032 type button battery, and evaluating the performance of the battery.
Performance testing
(1) Taking the button cell assembled in example 1 as an example, the deposition/exfoliation coulombic efficiency of the cells assembled with liquid metal modified current collectors and the nucleation overpotential of sodium metal on the liquid metal modified current collectors were evaluated using a charge and discharge device (nover CT-4008). Meanwhile, as a comparison, the above-described performance of the battery (comparative example) assembled with the bare aluminum foil current collector was also tested, and the results are shown in fig. 6 and 7. At a current density of 0.2mA/cm2In the next place, the nucleation overpotential (115.1mV) for metallic sodium on the liquid metal modified current collector is significantly lower than the nucleation overpotential (171.5mV) on the aluminum foil current collector. At a current density of 0.5mA/cm2The capacity is 0.5mAh/cm2The coulombic efficiency of the cell was tested under the conditions of (1). It can be seen that the cell assembled with the bare aluminum foil current collector has a low coulombic efficiency and is unstable and fluctuates severely up and down due to uneven sodium deposition and sodium dendrite growth. The coulombic efficiency of the battery assembled by the liquid metal modified current collector is higher, and the stability is improved, which shows that the growth of the sodium dendrite is effectively inhibited. The results show that after the aluminum foil is modified by the liquid metal, the coulomb efficiency of the battery is obviously improved, the stability is enhanced, and the growth of the sodium dendrite is effectively inhibited.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a sodium battery current collector is characterized in that a layer of room-temperature gallium-based liquid metal is smeared on the surface of metal aluminum, then standing is carried out for diffusion reaction, and an aluminum-gallium alloy layer is formed on the surface of the metal aluminum, so that the sodium battery current collector is obtained.
2. The preparation method according to claim 1, wherein the metallic aluminum comprises any one of aluminum foil, aluminum sheet, aluminum tape, aluminum wire, aluminum powder, aluminum block, aluminum wire, foamed aluminum, and aluminum mesh; the room-temperature gallium-based liquid metal is one of pure gallium, gallium-zinc alloy, gallium-indium-tin alloy and gallium-indium-tin-zinc alloy.
3. The method of claim 1, wherein the gallium-based room temperature liquid metal is applied to the aluminum metal in an amount of 0.05-10mg/cm 2.
4. The method of claim 1, wherein the diffusion reaction time is 0.1 to 10 hours and the reaction temperature is 5 ℃ to 80 ℃.
5. The sodium battery current collector manufactured according to the manufacturing method of any one of the preceding claims, comprising: metal aluminum and an aluminum-gallium alloy layer attached to the surface of the metal aluminum.
6. A metallic sodium electrode, characterized in that a certain amount of metallic sodium is electrodeposited on the current collector of the sodium battery as claimed in claim 5 by an electrodeposition method, and the metallic sodium electrode is obtained.
7. The sodium metal electrode of claim 6, wherein the cell composition during electrodeposition comprises a current collector, a sodium metal sheet, an electrolyte, a separator, and is assembled under an inert atmosphere.
8. The sodium metal electrode according to claim 7, wherein the electrolyte is one or more of ethers, esters and nitriles; the inert atmosphere is argon, nitrogen, hydrogen-argon mixed gas, helium or vacuum atmosphere, the oxygen content is less than 0.1ppm, and the moisture content is less than 0.1 ppm.
9. The sodium metal electrode of claim 6, wherein the deposition current is 0.05-20mA/cm2(ii) a The deposition capacity is 0.5-50mAh/cm2。
10. Use of a sodium metal electrode according to any one of claims 6 to 9 in the manufacture of sodium batteries, smart grids, electronics, electric cars, mobile energy storage devices.
CN202111395963.2A 2021-11-23 2021-11-23 Sodium battery current collector and preparation method and application thereof Pending CN114094114A (en)

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