CN113471446A - Iron-based current collector and preparation method and application thereof - Google Patents

Iron-based current collector and preparation method and application thereof Download PDF

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Publication number
CN113471446A
CN113471446A CN202110764745.5A CN202110764745A CN113471446A CN 113471446 A CN113471446 A CN 113471446A CN 202110764745 A CN202110764745 A CN 202110764745A CN 113471446 A CN113471446 A CN 113471446A
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iron
gallium
stainless steel
current collector
sodium
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冯金奎
魏传亮
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Shandong University
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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
    • H01M4/64—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
    • 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
    • H01M4/0402—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • 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
    • 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 belongs to the technical field of batteries, and particularly relates to an iron-based current collector, and a preparation method and application thereof. The wettability of the surface of the iron-based foil to metal cathodes such as lithium, sodium, potassium, calcium, magnesium and the like is improved, the uncontrollable growth of metal dendrites in the deposition process is inhibited, and the safety and the cycle life of a metal battery are further improved.

Description

Iron-based current collector and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an iron-based 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.
In recent years, with the rapid advance of new energy industries, lithium ion batteries using graphite as a negative electrode have been widely used in devices such as electric automobiles, smart grids, electric bicycles, smart watches, notebook computers, mobile phones, and the like. However, the lithium ion batteries commercialized at present cannot meet the demand of people due to low energy density. Therefore, the development of a rechargeable battery having high energy density, high safety, long life and low cost is imperative.
In recent years, researchers have attracted considerable attention because of their high energy density, such as lithium metal batteries, sodium metal batteries, potassium metal batteries, calcium metal batteries, and magnesium metal batteries, in which metal lithium, sodium, potassium, calcium, and magnesium are used as negative electrodes. The metal negative electrodes have the advantages of high theoretical specific capacity, low electrochemical potential, good conductivity and the like. However, these metal negative electrodes often use copper foil, aluminum foil, or titanium foil as a current collector. These collectors are not only costly, but also prone to uncontrolled growth of dendrites. The generation of dendrites not only reduces the life of the battery, but also causes a serious safety problem. Therefore, the current collector which is low in development cost and capable of inhibiting dendritic crystal growth can promote rapid progress of the rechargeable battery with high energy density, high safety, long service life and low cost, and has great significance for development of new energy industry.
Disclosure of Invention
In order to solve the problems in the prior art, the present disclosure provides an iron-based current collector, and a preparation method and an application thereof, wherein a current collector capable of inhibiting dendritic crystal growth is obtained through simple modification, and the method is simple and low in cost.
Specifically, the technical scheme of the present disclosure is as follows:
in a first aspect of the present disclosure, an iron-based current collector includes an iron-based substrate and a gallium-based liquid metal layer attached to a surface of the iron-based substrate.
In a second aspect of the present disclosure, a method for preparing an iron-based current collector obtains an iron-based substrate and a gallium-based liquid metal; gallium-based liquid metal is smeared on the surface of the iron-based substrate.
In a third aspect of the disclosure, an electrode sheet includes the iron-based current collector or the iron-based current collector prepared by the preparation method, and a metal negative electrode on the surface of the iron-based current collector.
In a fourth aspect of the disclosure, a method for preparing an electrode sheet is to obtain a metal layer of a metal negative electrode on the surface of the iron-based current collector or the iron-based current collector prepared by the preparation method by an electrochemical deposition method.
In a fifth aspect of the present disclosure, a sodium battery includes the iron-based current collector or the iron-based current collector manufactured by the preparation method, or the electrode sheet manufactured by the preparation method.
In a sixth aspect of the present disclosure, the iron-based current collector or the preparation method or the electrode sheet or the preparation method of the electrode sheet or the application of the battery in an energy storage device.
One or more technical schemes in the disclosure have the following beneficial effects:
(1) this openly adopts low price's iron-based foil as the mass flow body, can reduce the cost of battery.
(2) The green environment-friendly room-temperature gallium-based liquid metal is adopted as the surface modifier, so that the environment is not polluted.
(3) The method adopts a simple liquid metal coating process, and is easy to realize large-scale production and preparation.
(4) The method can form a compact and uniform room-temperature gallium-based liquid metal thin layer with good affinity for metal lithium, sodium, potassium, calcium, magnesium and the like on the surface of the iron-based current collector, can inhibit the growth of dendrites, and further improves the safety and the cycle life of a sodium battery.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1: a schematic flow diagram of a process for preparing a low-cost current collector capable of suppressing dendrite growth in examples 1-8 of the present disclosure is shown.
FIG. 2: the XRD patterns of the stainless steel foil and the liquid metallic gallium coated stainless steel foil of comparative example 1 and example 1 of the present disclosure are shown.
FIG. 3: is a scanning electron micrograph of the stainless steel foil of comparative example 1 of the present disclosure.
FIG. 4: is a scanning electron micrograph of the liquid metallic gallium coated stainless steel foil of example 1 of the present disclosure.
FIG. 5: is a scanning electron micrograph of the copper foil of comparative example 2 of the present disclosure.
FIG. 6: scanning electron microscope images of the deposition morphology of the metallic sodium on the surface of the stainless steel foil in comparative example 1 of the disclosure.
FIG. 7: is a scanning electron microscope image of the deposition morphology of the sodium metal on the surface of the liquid gallium metal-coated stainless steel foil in example 1 of the present disclosure.
FIG. 8: scanning electron microscope images of the deposition morphology of the sodium metal on the surface of the copper foil in comparative example 2 of the disclosure.
FIG. 9: a plot of sodium deposition/exfoliation coulombic efficiency for stainless steel foils, copper foils, and liquid metal gallium coated stainless steel foils of comparative examples 1, 2, and example 1 of the present disclosure.
Detailed Description
The disclosure is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
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. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
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 example embodiments according to the present disclosure. 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 the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
At present, copper foil, aluminum foil and titanium foil are generally used as current collectors of lithium, sodium, potassium, calcium, magnesium and other metal cathodes, dendritic crystals are easily generated, the cost is high, and the service life of a battery prepared by the traditional current collector is short.
In one embodiment of the present disclosure, an iron-based current collector includes an iron-based substrate and a gallium-based liquid metal layer attached to a surface of the iron-based substrate.
The gallium-based liquid metal (melting point 0-30 ℃) with high conductivity, low melting point, good fluidity and environment-friendly room temperature is coated on the surface of the iron-based current collector with low price. The gallium-based liquid metal can perform alloying reaction with metal lithium, sodium, potassium, calcium and magnesium to respectively generate lithium gallium, sodium gallium, potassium gallium, calcium gallium and magnesium gallium alloys. Namely, the gallium-based liquid metal has good wettability to the metal negative electrodes, and can be used as a nucleating agent to reduce the over-potential of metal deposition and inhibit the growth of dendrites. Thus, the liquid metal coating improves the wettability of the iron-based current collector surface to the metal negative electrode, which can inhibit uncontrolled growth of metal dendrites during deposition, thereby improving the safety and cycle life of the metal battery.
Modification of the iron-based current collector, which does not involve an alloy layer, is achieved by using gallium-based liquid metal. For a copper-based substrate, gallium-based liquid metal and a copper-based substrate are subjected to alloying reaction to obtain an alloy layer, and the characteristics of the alloy layer are utilized to obtain uniformly distributed active sites. However, unlike copper-based substrates, there has been no research for modifying iron-based substrates to prepare current collectors for the time being. When the ambient temperature is less than 100 ℃, the saturation concentration of iron in the gallium-based liquid metal is extremely low, and the solubility is lower than 0.1%. Therefore, the iron-based substrate does not have alloying reaction with the gallium-based liquid metal at the temperature of less than 100 ℃ and does not form an alloy layer with the gallium-based liquid metal. However, since the gallium-based liquid metal is very susceptible to alloying reactions with metals such as lithium, sodium, gallium, calcium, magnesium, and the like at room temperature. Therefore, the gallium-based liquid metal can be used as a nucleating agent when the metals are deposited, and form uniformly distributed nucleation active sites on the iron-based substrate, so that the nucleation overpotential of the metals when the metals are deposited on the iron-based substrate is reduced, the growth of dendrites is further inhibited, and uniform metal deposition is induced.
Furthermore, the load capacity of the gallium-based liquid metal on the iron-based substrate is 0.1-10mg/cm2。
Further, the iron-based substrate is selected from one of stainless steel, tinplate, pig iron and wrought iron; or the thickness of the gallium-based liquid metal layer is 0.5-10 μm. The gallium-based liquid metal layer behind the micron level not only can avoid excessive liquid metal loss and further reduce the cost, but also can avoid active metal loss caused by excessive alloying reaction between the gallium-based liquid metal layer and the metal cathode.
Further, the gallium-based liquid metal is selected from any one of gallium, gallium-zinc alloy, gallium-indium-tin alloy, and gallium-indium-tin-zinc alloy.
In one embodiment of the present disclosure, a method for preparing an iron-based current collector includes obtaining an iron-based substrate and a gallium-based liquid metal; gallium-based liquid metal is smeared on the surface of the iron-based substrate. The liquid metal coating process is simple and easy to implement, and the method has the advantage of low-cost planning production. In the preparation process, an alloy layer is formed without alloying treatment, and the method is simpler and faster.
Further, the preparation method is carried out at the temperature of 20-30 ℃.
In one embodiment of the disclosure, an electrode sheet comprises the iron-based current collector or the iron-based current collector prepared by the preparation method, and a metal negative electrode on the surface of the iron-based current collector; or the metal negative electrode is selected from any one of metal lithium, sodium, potassium, calcium and magnesium. A compact and uniform thin layer formed on the surface of the iron-based substrate has good affinity for metal lithium, sodium, potassium, calcium, magnesium and the like, can inhibit the growth of dendrites, and improves the safety and cycle life of the battery.
In one embodiment of the disclosure, in the preparation method of the electrode plate, a metal layer of a metal negative electrode is obtained on the surface of the iron-based current collector or the iron-based current collector prepared by the preparation method by an electrochemical deposition method; further, the deposition current is 0.05-20mA/cm2(ii) a The deposition capacity is 0.1-50mAh/cm2. Under the deposition condition, the generation of dendrites is also favorably avoided.
In an embodiment of the disclosure, a sodium battery comprises the iron-based current collector or the iron-based current collector prepared by the preparation method or the electrode plate prepared by the preparation method. The electrolyte of the battery is any one of esters, ethers, nitriles and the like. Based on the modified current collector as an electrode, the modified current collector can avoid the generation of dendrites in the sodium battery, and the safety of the battery is improved. Based on the current collector, the cycle stability of the sodium battery is greatly improved. Meanwhile, the cost of the iron-based current collector is low, so that the cost of the battery is greatly reduced.
In one embodiment of the present disclosure, the iron-based current collector or the preparation method or the electrode sheet or the preparation method of the electrode sheet or the application of the battery in an energy storage device. The method can inhibit the growth of dendritic crystals in the metal battery and reduce the cost of the battery, so that the method is expected to be practically applied to an energy storage device in the future, and further promotes the development of new energy industries and social progress.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
An iron-based current collector comprising the steps of (fig. 1):
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface. The XRD and scanning electron micrographs are shown in FIGS. 2 and 3.
(2) Using dust-free paperQuickly coating a layer of liquid metal gallium on the surface of the cleaned stainless steel foil, wherein a scanning electron microscope of the liquid metal gallium is shown in figure 4, and the loading amount of the gallium is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a stainless steel foil coated with liquid metal gallium as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of a current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a stainless steel foil coated with liquid metal gallium, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metallic gallium coated stainless steel foil2The scanning electron micrograph of the metal sodium of (2) is shown in FIG. 7.
(5) And (4) disassembling the battery with the sodium deposited in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium with the sodium deposited.
(6) Liquid metal gallium coated stainless steel foil with sodium deposited as the negative electrode was matched with sodium vanadium phosphate positive electrode material to make CR2032 type button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium coated stainless steel foil deposited with sodium, a sodium vanadium phosphate positive electrode, 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Example 2
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the tinplate foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium on the surface of the cleaned tinplate foil by using dust-free paper. The loading amount of gallium is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte, using liquid metal gallium coated tinplate as positive electrode, and metal sodium sheet as negative electrodeThe half cells were assembled to evaluate the electrochemical performance of the current collectors. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a tinplate coated with liquid metal gallium, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metal gallium coated tinplate2The metal sodium of (1).
(5) And (4) disassembling the battery with the sodium deposited in the step (4), and taking out the tinplate coated with the liquid metal gallium with the sodium deposited.
(6) The tin foil coated with liquid metal gallium deposited with sodium as a negative electrode was matched with a sodium iron phosphate positive electrode material to form a CR2032 button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a tinplate coated with liquid metal gallium deposited with sodium, a sodium iron phosphate positive electrode, 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and polypropylene separator.
Example 3
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the white iron foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium on the surface of the cleaned white iron foil by using dust-free paper. The loading amount of gallium is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a white iron foil coated with liquid metal gallium as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, white iron foil coated with liquid metal gallium, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Current density of 0.5m was deposited on liquid metal gallium coated white iron foilAh/cm2The metal sodium of (1).
(5) And (4) disassembling the battery with the sodium deposited in the step (4), and taking out the white iron foil coated with the liquid metal gallium with the sodium deposited.
(6) A white iron foil coated with liquid metal gallium with sodium deposited was used as a negative electrode to match with a sodium vanadium fluorophosphate positive electrode material to assemble a CR2032 type button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), white iron foil coated with liquid metal gallium deposited with sodium, a sodium vanadium fluorophosphate positive electrode, 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Example 4
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium-zinc alloy on the surface of the cleaned stainless steel foil by using dust-free paper. The loading amount of the gallium-zinc alloy is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a stainless steel foil coated with liquid metal gallium-zinc alloy as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a stainless steel foil coated with liquid metal gallium zinc alloy, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Is deposited at a current density of 0.5mAh/cm on a liquid metal gallium-zinc alloy coated stainless steel foil2The metal sodium of (1).
(5) And (4) disassembling the battery deposited with sodium in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium-zinc alloy deposited with sodium.
(6) Matching the stainless steel foil coated with the liquid metal gallium-zinc alloy deposited with sodium as a negative electrode with the ferric fluoride phosphate sodium positive electrode material to obtain CRModel 2032 button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium-zinc alloy coated stainless steel foil deposited with sodium, a sodium iron fluoride phosphate positive electrode, 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Example 5
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium indium tin alloy on the surface of the cleaned stainless steel foil by using dust-free paper. The loading amount of the gallium-zinc alloy is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a stainless steel foil coated with liquid metal gallium indium tin alloy as a positive electrode and a metal sodium sheet as a negative electrode in EC/EMC-5% FEC liquid electrolyte so as to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a stainless steel foil coated with liquid metal gallium indium tin alloy, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metal gallium indium tin alloy coated stainless steel foil2The metal sodium of (1).
(5) And (4) disassembling the battery with the sodium deposited in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium indium tin alloy with the sodium deposited.
(6) The liquid metal gallium indium tin alloy coated stainless steel foil deposited with sodium is used as a cathode and matched with manganese iron sodium phosphate cathode material to form a CR2032 type button full cell so as to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium indium tin alloy coated stainless steel foil deposited with sodium, a manganese iron sodium phosphate positive electrode, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolysisLiquid and fiberglass separators.
Example 6
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium on the surface of the cleaned stainless steel foil by using dust-free paper. The loading amount of gallium is 1mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a stainless steel foil coated with liquid metal gallium as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of a current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a stainless steel foil coated with liquid metal gallium, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metallic gallium coated stainless steel foil2The metal sodium of (1).
(5) And (4) disassembling the battery with the sodium deposited in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium with the sodium deposited.
(6) Liquid metal gallium coated stainless steel foil with sodium deposited as the negative electrode was matched with sodium vanadium phosphate positive electrode material to make CR2032 type button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium coated stainless steel foil deposited with sodium, a sodium vanadium phosphate positive electrode, 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Example 7
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) Rapidly applying dust-free paper on the cleaned surface of the stainless steel foilAnd coating a layer of liquid metal gallium. The loading amount of gallium is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 type button cell in 1M-LiPF6The half-cell was assembled with a liquid metal gallium coated stainless steel foil as the positive electrode and a metal lithium sheet as the negative electrode in an EC/DEC-10% FEC liquid electrolyte to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a lithium sheet, a liquid metal gallium-coated stainless steel foil and 1M-LiPF6EC/DEC-10% FEC liquid electrolyte and polypropylene separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metallic gallium coated stainless steel foil2The metal lithium of (1).
(5) And (4) disassembling the battery with the lithium deposited in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium with the lithium deposited.
(6) And matching the stainless steel foil coated with liquid metal gallium deposited with lithium as a negative electrode with a lithium iron phosphate positive electrode material to form a CR2032 button type full cell so as to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium coated stainless steel foil deposited with lithium, a lithium iron phosphate positive electrode, 1M-LiPF6EC/DEC-10% FEC liquid electrolyte and polypropylene separator.
Example 8
An iron-based current collector comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface.
(2) And (3) rapidly coating a layer of liquid metal gallium on the surface of the cleaned stainless steel foil by using dust-free paper. The loading amount of gallium is 0.2mg/cm2。
(3) Under inert atmosphere, using CR2032 button cell at 0.8M-KPF6The half-cell was assembled with liquid metal gallium coated stainless steel foil as positive electrode and potassium metal sheet as negative electrode in EC/DEC liquid electrolyte to evaluate the electrochemical performance of the current collector. Button cell structure comprises positive electrode shell (stainless steel)Negative electrode casing (stainless steel), gasket (stainless steel), potassium sheet, liquid metal gallium coated stainless steel foil, 0.8M-KPF6EC/DEC liquid electrolyte and glass fiber separator.
(4) At 0.2mA/cm2Current density of 0.5mAh/cm on liquid metallic gallium coated stainless steel foil2The metal potassium of (2).
(5) And (4) disassembling the battery with potassium deposited in the step (4), and taking out the stainless steel foil coated with the liquid metal gallium with potassium deposited.
(6) A CR2032 type button full cell was assembled with a stainless steel foil coated with liquid metal gallium deposited with potassium as the negative electrode matched with a prussian blue positive electrode material to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a liquid metal gallium coated stainless steel foil deposited with potassium, a Prussian blue positive electrode, and 0.8M-KPF6EC/DEC liquid electrolyte and glass fiber separator.
Comparative example 1
The implementation of comparative example 1 mainly comprises the following steps:
(1) and (3) cleaning the surface of the stainless steel foil by using absolute ethyl alcohol to remove oil stains on the surface. The scanning electron microscope is shown in FIG. 3.
(2) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a stainless steel foil as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a stainless steel foil and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(3) At 0.2mA/cm2Current density of 0.5mAh/cm deposited on stainless steel foil2The scanning electron micrograph of the metal sodium of (2) is shown in FIG. 6.
(4) And (4) disassembling the battery with the sodium deposited in the step (3), and taking out the stainless steel foil with the sodium deposited.
(5) The stainless steel foil deposited with sodium is used as a cathode and matched with the vanadium sodium phosphate anode material to form CR2032 type button full cell to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a stainless steel foil deposited with sodium, a sodium vanadium phosphate positive electrode, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Comparative example 2:
the difference from comparative example 1 is that the iron-based substrate was replaced with the copper-based substrate. The implementation mainly comprises the following steps:
(1) and (3) cleaning the surface of the copper foil by using absolute ethyl alcohol to remove oil stains on the surface. The scanning electron microscope is shown in FIG. 5.
(2) Under inert atmosphere, using CR2032 button cell in 1M-NaPF6And (4) assembling a half cell by taking a copper foil as a positive electrode and a metal sodium sheet as a negative electrode in an EC/EMC-5% FEC liquid electrolyte to evaluate the electrochemical performance of the current collector. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a sodium sheet, a copper foil and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
(3) At 0.2mA/cm2The current density of the copper foil is 0.5mAh/cm2The scanning electron micrograph of the metal sodium of (2) is shown in FIG. 8.
(4) And (4) disassembling the battery with the sodium deposited in the step (3), and taking out the copper foil with the sodium deposited.
(5) Copper foil with sodium deposited is used as a negative electrode and matched with a sodium vanadium phosphate positive electrode material to form a CR2032 type button full cell so as to evaluate the electrochemical performance of the full cell. The button type full cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a copper foil deposited with sodium, a sodium vanadium phosphate positive electrode, and 1M-NaPF6-EC/EMC-5% FEC liquid electrolyte and glass fibre separator.
Performance testing
(1) The sodium deposition/exfoliation coulombic efficiency of liquid metal gallium coated stainless steel foil was evaluated using a charge and discharge device (nover CT-4008) using the assembled button half cell of example 1 as an example. Also, as a comparison, the blank stainless steel foil and copper foil assembled halves were also tested separatelyThe above-described properties of the batteries (comparative examples 1 and 2) were obtained, and the results are shown in fig. 9. At a current density of 1mA/cm2Capacity of 1mAh/cm2The coulombic efficiency of the half cell was tested under the condition that the charge cut-off voltage was 0.5V.
It can be seen that the coulomb efficiency of the current collector is significantly improved after the liquid metal gallium is modified. The poor coulombic efficiency of stainless steel foils is caused by severe side reactions initiated by the uncontrolled growth of sodium dendrites. The blank stainless steel foil has poor affinity for metallic sodium and produces a large nucleation overpotential during sodium deposition. A larger nucleation overpotential promotes the growth of sodium dendrites. The gallium-based liquid metal has good affinity for sodium and can form an alloy with sodium metal. After coating the stainless steel foil with the sodium-philic liquid metal, the surface becomes sodium-philic, the sodium deposition overpotential is reduced and the growth of sodium dendrites is limited. Thus, the coulombic efficiency of the liquid metallic gallium coated stainless steel foil is higher than that of the blank stainless steel. The average coulombic efficiency of the stainless steel was 77.3% over 100 cycles, while the average coulombic efficiency of the liquid metallic gallium coated stainless steel foil was 88.0%. In current literature reports, copper foil current collectors are in similar electrolytes (e.g., 1M-NaPF)6EC/EMC) is mostly below 50%, the cycle times are below 50.
To further illustrate, the specificity of the iron-based substrate for the sodium cell, coulombic efficiency tests were also performed on the current collector obtained in comparative example 2, with the results shown in fig. 9. The average coulombic efficiency of the copper foil current collector was only 69.1% over the 100 cycle range, significantly lower than that of stainless steel and liquid metal coated stainless steel. Copper foil is less coulombic than stainless steel and liquid metal gallium coated stainless steel foils primarily because its surface is rougher, has more defects, is not sodium philic, and results in more severe dendrite growth.
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 changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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.

Claims (10)

1. An iron-based current collector is characterized by comprising an iron-based substrate and a gallium-based liquid metal layer attached to the surface of the iron-based substrate.
2. An iron-based current collector as claimed in claim 1 wherein the gallium-based liquid metal is present in an amount of 0.1 to 10mg/cm on the iron-based substrate2。
3. An iron-based current collector as claimed in claim 1, wherein said iron-based substrate is selected from one of stainless steel, tin plate, pig iron, and wrought iron; or the thickness of the gallium-based liquid metal layer is 0.5-10 μm.
4. An iron-based current collector as claimed in claim 1, wherein said gallium-based liquid metal is selected from any one of gallium, gallium-zinc alloy, gallium-indium-tin-zinc alloy.
5. A preparation method of an iron-based current collector is characterized by obtaining an iron-based substrate and gallium-based liquid metal; gallium-based liquid metal is smeared on the surface of the iron-based substrate.
6. The method of claim 5, wherein the method is performed at 20-30 ℃.
7. An electrode sheet, characterized by comprising the iron-based current collector of any one of claims 1 to 4 or the iron-based current collector prepared by the preparation method of claim 5 or 6, and a metal negative electrode on the surface of the iron-based current collector; or the metal negative electrode is selected from any one of metal lithium, sodium, potassium, calcium and magnesium.
8. A preparation method of an electrode slice, which is characterized in that a metal layer of a metal negative electrode is obtained on the surface of the iron-based current collector in any one of claims 1 to 4 or the iron-based current collector prepared by the preparation method in claim 5 or 6 by an electrochemical deposition method; further, the deposition current is 0.05-20mA/cm2(ii) a The deposition capacity is 0.1-50mAh/cm2。
9. A sodium battery, comprising the iron-based current collector according to any one of claims 1 to 4, or the iron-based current collector manufactured by the manufacturing method according to claim 5 or 6, or the electrode sheet according to claim 7, or the electrode sheet manufactured by the manufacturing method according to claim 8.
10. Use of the iron-based current collector of any one of claims 1-4, or the preparation method of claim 5 or 6, or the electrode sheet of claim 7, or the preparation method of claim 8, or the battery of claim 9 in an energy storage device.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114242931A (en) * 2021-11-12 2022-03-25 欣旺达电动汽车电池有限公司 Method for improving battery cell pole piece and performance

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08162109A (en) * 1994-12-02 1996-06-21 Dowa Mining Co Ltd Ga coated type or surface covered type negative electrode and secondary battery using the same
US20130045427A1 (en) * 2011-08-19 2013-02-21 Nanoteck Instruments, Inc. Prelithiated current collector and secondary lithium cells containing same
CN110752375A (en) * 2019-10-31 2020-02-04 山东大学 Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof
CN110911689A (en) * 2019-10-31 2020-03-24 南方科技大学 Current collector and preparation method thereof, electrode plate and secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08162109A (en) * 1994-12-02 1996-06-21 Dowa Mining Co Ltd Ga coated type or surface covered type negative electrode and secondary battery using the same
US20130045427A1 (en) * 2011-08-19 2013-02-21 Nanoteck Instruments, Inc. Prelithiated current collector and secondary lithium cells containing same
CN110752375A (en) * 2019-10-31 2020-02-04 山东大学 Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof
CN110911689A (en) * 2019-10-31 2020-03-24 南方科技大学 Current collector and preparation method thereof, electrode plate and secondary battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114242931A (en) * 2021-11-12 2022-03-25 欣旺达电动汽车电池有限公司 Method for improving battery cell pole piece and performance

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