CN116613283A - Lithium metal negative electrode and preparation method and application thereof - Google Patents

Lithium metal negative electrode and preparation method and application thereof Download PDF

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Publication number
CN116613283A
CN116613283A CN202310731010.1A CN202310731010A CN116613283A CN 116613283 A CN116613283 A CN 116613283A CN 202310731010 A CN202310731010 A CN 202310731010A CN 116613283 A CN116613283 A CN 116613283A
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alloy
metal matrix
lithium
porous metal
porous
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王宝
耿海涛
李文彪
郑淑敏
冯丹
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Institute of Process Engineering of CAS
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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
    • H01M4/13—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a lithium metal anode and a preparation method and application thereof. The preparation method comprises the following steps: and carrying out vacuum dealloying treatment on the alloy sheet to obtain a porous metal matrix decorated by the multi-element alloy, and pouring molten lithium metal into the porous metal matrix decorated by the multi-element alloy to obtain a lithium metal negative electrode of the porous metal matrix decorated by the multi-element alloy. The lithium metal anode of the multi-element alloy modified porous metal matrix prepared by the method can exert the advantages of the three-dimensional porous metal matrix in terms of volume expansion inhibition and the advantages of the porous metal matrix in terms of local current density reduction and dendrite growth inhibition.

Description

Lithium metal negative electrode and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a lithium metal negative electrode, a preparation method and application thereof, and in particular relates to a multi-element alloy modified porous metal matrix lithium metal negative electrode, a preparation method and application thereof.
Background
The lithium metal cathode has high theoretical specific capacity (3860 mAh g) -1 ) Low electrochemical redox potential (-3.04V vs SHE) and low density (0.53 g cm) -3 ) Is considered as a "holy cup" of the negative electrode material of the next-generation secondary lithium battery. However, the problem of thermal runaway caused by lithium dendrite growth and volume expansion severely hampers commercialization of lithium metal anodes. After the battery is charged and discharged for many times, dendrites growing on the surface of the lithium metal negative electrode can puncture the diaphragm, so that short circuit is caused, and the safety problem of the battery is caused. In addition, dendrite growth can lead to dead lithium and slow the diffusion rate of lithium. At the same time, the infinite volume expansion of lithium metal will exhibit a porous structure. Therefore, limiting the infinite volume expansion of lithium and inhibiting lithium dendrite growth is of great importance for commercial applications in lithium metal batteries.
To solve the above problems, researchers have proposed four main strategies: (1) Regulating and controlling electrolyte components, concentration and additives to change components of a solid electrolyte interface on the surface of lithium metal and regulate the deposition behavior of the lithium metal so as to inhibit the growth of lithium dendrites; (2) A layer of artificial SEI with uniform and stable structure and ion conduction and electronic insulation is constructed on the surface of the metal lithium, so that the deposition behavior of the lithium can be effectively regulated and controlled, and the growth of dendrites can be inhibited; (3) Modification of commercial membranes can improve the membrane's dendrite stress resistance and regulate dendrite growth behavior; (4) The three-dimensional conductive framework is designed for pre-storing lithium matrix to inhibit growth of lithium dendrites. The three-dimensional conductive framework not only can limit infinite volume expansion of lithium, but also can homogenize lithium ion flow and inhibit growth of lithium dendrite, and is a key for improving safety and stability of lithium metal.
CN108365178A discloses a protection method for lithium metal negative electrode, lithium metal negative electrode and lithium battery. The preparation method comprises the steps of forming a protective layer on the surface of a lithium metal negative electrode, dispersing an anionic polymer and boron nitride in an organic solvent to prepare a dispersion liquid, coating the dispersion liquid on the surface of the lithium metal negative electrode, and forming the protective layer on the surface of the lithium metal negative electrode after drying. The selective conduction of lithium ions can be realized through the composite protective layer, and the lithium ions can be uniformly deposited on the surface of the lithium metal negative electrode.
CN114388746a discloses a lithium metal negative electrode, a lithium metal battery, a preparation method thereof and a method for inhibiting lithium dendrite. And arranging a carbon material layer on the surface of the metal lithium sheet, and processing the metal lithium sheet carrying the carbon material layer into a lithium metal anode.
However, in the above patent, a protective layer or a carbon material layer is provided on the surface of the lithium metal negative electrode, so that the lithium dendrite can be suppressed, but the resistance of the negative electrode is increased.
Therefore, how to prepare a lithium metal anode with low resistance and capable of inhibiting the growth of lithium dendrites is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a lithium metal negative electrode and a preparation method and application thereof, in particular to a lithium metal negative electrode with a multi-element alloy modified porous metal matrix and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of a lithium metal anode with a multi-element alloy modified porous metal matrix, which comprises the following steps:
and performing vacuum dealloying treatment on the alloy sheet to obtain a porous metal matrix decorated by the multi-element alloy, and diffusing molten lithium metal into the porous metal matrix decorated by the multi-element alloy to obtain a lithium metal negative electrode of the porous metal matrix decorated by the multi-element alloy.
The three-dimensional lithium metal composite negative electrode is prepared by using porous metal as a current collector, modifying a multi-element alloy with affinity to lithium on the surface of a porous metal matrix by a vacuum dealloying method, and combining a hot injection method of molten lithium. The prepared multi-element alloy modified porous metal matrix lithium metal anode can exert the advantages of the three-dimensional porous metal matrix in terms of volume expansion inhibition and the advantages of the porous metal matrix in terms of local current density reduction and dendrite growth inhibition.
As a preferable technical scheme of the invention, the preparation method of the alloy sheet comprises the following steps:
and preparing a multi-element alloy precursor by adopting high-frequency induction heating equipment, and cutting the multi-element alloy precursor to obtain an alloy sheet.
Preferably, the multi-element alloy precursor includes any one of an alloy element and a copper element, an alloy element and a nickel element, or a combination of an alloy element, a copper element and a nickel element.
Preferably, the alloying elements in the multi-element alloy precursor include any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine, or iodine, wherein typical but non-limiting examples of such combinations are: a combination of magnesium and calcium, a combination of strontium and barium, a combination of scandium and iridium, a combination of ruthenium and palladium, a combination of silver and cadmium, a combination of yttrium and platinum, a combination of gold and zinc, a combination of mercury and aluminum, a combination of gallium and indium, a combination of thallium and germanium, a combination of tin and lead, a combination of carbon and silicon, a combination of arsenic and antimony, a combination of bismuth and antimony, a combination of nitrogen and phosphorus, a combination of oxygen and sulfur, a combination of selenium and fluorine, a combination of fluorine and chlorine, a combination of bismuth and bromine, or a combination of iodine and phosphorus, and the like.
As a preferred technical scheme of the invention, the vacuum dealloying method comprises the following steps: fixing the alloy sheet in a tube furnace, and completing vacuum dealloying by setting vacuum degree, heat preservation temperature and heat preservation time.
Preferably, the vacuum degree is less than or equal to 5 multiplied by 10 -3 Pa, wherein the vacuum degree may be 1X 10 -3 Pa、2×10 -3 Pa、3×10 -3 Pa、4×10 -3 Pa or 5X 10 -3 Pa, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature is 700 to 900 ℃, wherein the temperature may be 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the incubation time is 2 to 4 hours, wherein the time may be 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3.0 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, or 4 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the porous metal matrix in the multi-element alloy modified porous metal matrix includes any one or a combination of at least two of porous copper, porous nickel copper alloy, porous copper alloy or porous nickel alloy, wherein typical but non-limiting examples of the combination are: a combination of porous copper and porous nickel, a combination of porous nickel and porous nickel-copper alloy, a combination of porous nickel-copper alloy and porous copper alloy, or a combination of porous copper alloy and porous nickel alloy, etc.
Preferably, the porous copper alloy includes copper element and alloy element.
Preferably, the porous nickel alloy includes nickel element and an alloying element.
As a preferred embodiment of the present invention, the alloying elements in the porous metal matrix modified by the multi-element alloy include any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine, or iodine, wherein the combination is typically but not limited to: a combination of magnesium and calcium, a combination of strontium and barium, a combination of scandium and iridium, a combination of ruthenium and palladium, a combination of silver and cadmium, a combination of yttrium and platinum, a combination of gold and zinc, a combination of mercury and aluminum, a combination of gallium and indium, a combination of thallium and germanium, a combination of tin and lead, a combination of carbon and silicon, a combination of arsenic and antimony, a combination of bismuth and antimony, a combination of nitrogen and phosphorus, a combination of oxygen and sulfur, a combination of selenium and fluorine, a combination of fluorine and chlorine, a combination of bismuth and bromine, or a combination of iodine and tin, and the like.
According to the preferred technical scheme, after the vacuum dealloying treatment, volatile elements are removed, and the porous metal matrix modified by the multi-element alloy is obtained.
Preferably, the volatile element comprises any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine, or iodine, wherein typical but non-limiting examples of the combination are: a combination of magnesium and calcium, a combination of strontium and barium, a combination of scandium and iridium, a combination of ruthenium and palladium, a combination of silver and cadmium, a combination of yttrium and platinum, a combination of gold and zinc, a combination of mercury and aluminum, a combination of gallium and indium, a combination of thallium and germanium, a combination of tin and lead, a combination of carbon and silicon, a combination of arsenic and antimony, a combination of bismuth and antimony, a combination of nitrogen and phosphorus, a combination of oxygen and sulfur, a combination of selenium and fluorine, a combination of fluorine and chlorine, a combination of bismuth and bromine, or a combination of iodine and tin, and the like.
Preferably, the volatile element comprises >65 atomic percent of the multi-element alloy precursor, wherein the atomic percent may be 66%, 67%, 68%, 69%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, or 90%, etc., but is not limited to the recited values, as other non-recited values within the range are equally applicable.
According to a preferred technical scheme of the invention, the preparation method of the molten lithium comprises the step of carrying out melting treatment on metal lithium to obtain the molten lithium.
Preferably, the melting treatment is performed on a heating plate.
Preferably, the temperature of the melting treatment is not less than 180 ℃, wherein the temperature may be 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the atmosphere of the melt processing includes an argon atmosphere.
As a preferred embodiment of the present invention, the molten lithium is loaded by contacting the porous metal substrate modified with a multi-element alloy with the molten lithium.
Preferably, the multi-element alloy-modified porous metal substrate has a melting point higher than the temperature of the heating plate.
In a preferred embodiment of the present invention, the porous metal substrate modified with the multi-element alloy has a pore diameter of 2 to 10. Mu.m, wherein the pore diameter may be 2. Mu.m, 3. Mu.m, 4. Mu.m, 5. Mu.m, 6. Mu.m, 7. Mu.m, 8. Mu.m, 9. Mu.m, 10. Mu.m, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The second object of the present invention is to provide a lithium metal anode of a porous metal matrix modified with a multi-element alloy, which is prepared by the preparation method according to one of the objects, wherein the lithium metal anode comprises a porous metal matrix and lithium metal filled in pores of the porous metal matrix, and the pores of the porous metal matrix are modified with a multi-element alloy.
Another object of the present invention is to provide a lithium metal battery comprising the multi-element alloy-modified porous metal-based lithium metal anode as defined in the second object.
Compared with the prior art, the invention has the following beneficial effects:
(1) The multi-element alloy modified porous metal matrix lithium metal anode prepared by the method has stable structure, is beneficial to limiting the infinite volume expansion of lithium, and can effectively prevent the lithium anode from loosening and powdering;
(2) The lithium metal negative electrode of the multi-element alloy modified porous metal matrix prepared by the method has higher electron conductivity, and provides favorable conditions for electron conduction in a bulk phase;
(3) The modification of the lithium-philic multi-element alloy on the porous metal matrix in the lithium metal negative electrode of the multi-element alloy modified porous metal matrix prepared by the method is favorable for inducing uniform deposition of lithium, so that growth of lithium dendrites is inhibited;
(4) The multi-element alloy in the multi-element alloy modified porous metal matrix lithium metal negative electrode prepared by the method is used as a lithium-philic substance, is not easy to fall off in the battery cycle process, does not influence the lithium-philic effect, has good conductivity, does not reduce the electronic conductivity of a lithium host, can induce lithium ion deposition in the battery charging and discharging process, effectively inhibits dendrite growth in the lithium metal battery, and greatly improves the electrochemical performance of the lithium metal battery;
(5) After the lithium metal negative electrode of the multi-element alloy modified porous metal matrix is modified by the lithium-philic multi-element alloy, the effective current density on the surface is reduced, so that lithium ions flow uniformly, and the growth of lithium dendrites is inhibited.
Drawings
FIG. 1 is an SEM image of a multi-component alloy-modified porous metal matrix of example 1 of the invention.
Fig. 2 is an SEM image of a lithium metal anode of a multi-alloy modified porous metal matrix of example 1 of the present invention.
Fig. 3 is a graph of the rate performance of a full cell of a lithium metal negative electrode matching lithium iron phosphate positive electrode of the multi-component alloy modified porous metal matrix of example 1 of the present invention.
Fig. 4 is a graph of the cycling performance of a full cell of a lithium metal negative electrode matching lithium iron phosphate positive electrode of the multi-component alloy modified porous metal matrix of example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium metal anode with a porous metal matrix modified by a multi-element alloy and a preparation method thereof. The multi-element alloy is copper-tin alloy, and the porous metal matrix is porous copper, namely a lithium metal anode of the porous copper decorated by the copper-tin alloy.
The preparation method of the copper-tin alloy modified porous copper comprises the following steps: the porous copper decorated by copper-tin alloy is prepared by vacuum dealloying method, firstly, the metal raw materials (brass H59, zinc and tin) are respectively cleaned by alcohol and deionized water by ultrasonic, and dried at 60 ℃. Preparation of Cu by smelting raw materials using high frequency induction heating apparatus 24.7 Sn 1.3 Zn 74 An alloy ingot. Cutting alloy ingots using a fast wire cutting machineCut into round alloy pieces (diameter 15mm, thickness 350 μm). Then fixing the alloy sheet in a tube furnace for 3 hours for vacuum heat treatment, wherein the vacuum degree is less than 1 multiplied by 10 -3 Pa, the heat treatment temperature is 750 ℃, and the zinc element volatilizes during the heat treatment process, so that the copper-tin alloy modified porous copper is obtained, as shown in figure 1.
The preparation method of the copper-tin alloy modified porous copper lithium metal anode comprises the following steps: the lithium sheet is placed on a heating plate with the heating temperature of 240 ℃ to be melted into molten lithium metal, and then the porous copper decorated by copper-tin alloy is placed on the surface of the molten lithium metal. The lithium metal will diffuse throughout the porous copper interior to form a three-dimensional lithium metal anode as shown in fig. 2.
The negative electrode in example 1 was assembled into a lithium ion battery, wherein the positive electrode of the battery was lithium iron phosphate, the battery performance of example 1 was tested by using a CR 2032 button cell model in electrochemical test, the diameter of the positive electrode lithium iron phosphate pole piece was 12mm, the diameter of the lithium metal negative electrode was 14.5mm, and the electrolyte was an ester electrolyte (1M lithium hexafluorophosphate (LiPF 6 ) Dissolved in Ethylene Carbonate (EC)/diethyl carbonate (DEC), v/v). The separator was Celgard 2400 under the test conditions of 0.1C,0.2C,0.5C,1.0C,2.0C,5.0C and 0.1C rate tests.
The rate test result of the assembled full battery of the lithium metal cathode matching lithium iron phosphate anode synthesized in example 1 is shown in FIG. 3, and the discharge specific capacity of the full battery of lithium metal at 0.1C is 161.8mAh g -1 Specific discharge capacity at 0.2C was 153.8mAh g -1 The specific discharge capacity at 0.5C was 148.5mAh g -1 The specific discharge capacity at 1.0C was 137.3mAh g -1 Specific discharge capacity at 2.0C was 121.8mAh g -1 The specific discharge capacity at 5.0C was 96.8mAh g -1 When the multiplying power is restored to 0.1C, 156.6mAh g still exists -1 Exhibits excellent rate performance at different rates.
The long-cycle test result of the lithium metal anode-lithium iron phosphate anode assembled full battery synthesized in example 1 is shown in fig. 4, and the initial discharge specific capacity of the lithium metal full battery in the long-cycle test of 10C is 89.7mAh g -1 After 1000 circles, putThe specific electric capacity is reduced to 64.1mAh g -1 The circulation is stable after that, and the excellent circulation stability and higher capacity retention rate are shown, and the coulombic efficiency is more than 99%.
Comparative example 1
This comparative example directly uses a commercial lithium metal sheet as the negative electrode, and the other conditions are the same as in example 1.
The negative electrode in example 1 was replaced with the negative electrode of this comparative example, and a lithium ion battery was assembled in the same manner.
The lithium ion batteries assembled with the negative electrodes in example 1 and comparative example 1 were subjected to a test for 10C long-cycle charge-discharge cycle performance, and the test results are shown in table 1.
TABLE 1
Initial discharge specific capacity (mAh g) -1 ) Specific discharge capacity (mAh g) after 1000 cycles -1 )
Example 1 89.7 64.1
Comparative example 1 77.3 38.6
The table can be obtained by: compared with a metal lithium sheet, the multi-element alloy modified porous metal matrix lithium metal anode provided by the invention has excellent cycle stability and higher capacity retention rate.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (10)

1. A method for preparing a lithium metal negative electrode of a multi-element alloy modified porous metal matrix, which is characterized by comprising the following steps:
and carrying out vacuum dealloying treatment on the alloy sheet to obtain a porous metal matrix decorated by the multi-element alloy, and pouring molten lithium metal into the porous metal matrix decorated by the multi-element alloy to obtain a lithium metal negative electrode of the porous metal matrix decorated by the multi-element alloy.
2. The method of manufacturing as claimed in claim 1, wherein the method of manufacturing the alloy sheet comprises: preparing a multi-element alloy precursor by adopting high-frequency induction heating equipment, and cutting the multi-element alloy precursor to obtain an alloy sheet;
preferably, the multi-element alloy precursor includes any one of an alloy element and a copper element, an alloy element and a nickel element, or a combination of an alloy element, a copper element and a nickel element;
preferably, the alloying elements in the multi-element alloy precursor comprise any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine, or iodine.
3. The production method according to claim 1 or 2, characterized in that the vacuum dealloying method comprises: fixing the alloy sheet in a tube furnace, and completing vacuum dealloying by setting vacuum degree, heat preservation temperature and heat preservation time;
preferably, the vacuum degree is less than or equal to 5 multiplied by 10 -3 Pa；
Preferably, the heat preservation temperature is 700-900 ℃;
preferably, the heat preservation time is 2-4 h.
4. A method of preparing according to any one of claims 1 to 3, wherein the porous metal matrix of the multi-element alloy modified porous metal matrix comprises any one or a combination of at least two of porous copper, porous nickel copper alloy, porous copper alloy, or porous nickel alloy;
preferably, the porous copper alloy includes copper element and alloy element;
preferably, the porous nickel alloy includes nickel element and an alloying element.
5. The method of claim 4, wherein the alloying elements in the multi-component alloy-modified porous metal matrix comprise any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine, or iodine.
6. The method according to any one of claims 1 to 5, wherein after the vacuum dealloying treatment, volatile elements are removed to obtain the porous metal matrix modified by the multi-element alloy;
preferably, the volatile element comprises any one or a combination of at least two of magnesium, calcium, strontium, barium, scandium, iridium, ruthenium, palladium, silver, cadmium, yttrium, platinum, gold, zinc, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, carbon, silicon, arsenic, antimony, bismuth, antimony, nitrogen, phosphorus, oxygen, sulfur, selenium, fluorine, chlorine, bromine or iodine;
preferably, the volatile element comprises >65 atomic percent of the multi-element alloy precursor.
7. The method according to any one of claims 1 to 6, wherein the method for producing molten lithium comprises subjecting metallic lithium to a melting treatment to obtain the molten lithium;
preferably, the melting treatment is performed on a heating plate;
preferably, the temperature of the melting treatment is more than or equal to 180 ℃;
preferably, the atmosphere of the melt processing includes an argon atmosphere.
8. The method of claim 7, wherein the loading of molten lithium is performed by contacting a porous metal matrix modified with a multi-element alloy with the molten lithium;
preferably, the melting point of the multi-element alloy-modified porous metal substrate is higher than the temperature of the heating plate;
preferably, the pore diameter of the porous metal matrix modified by the multi-element alloy is 2-10 mu m.
9. A lithium metal anode of a multi-element alloy modified porous metal matrix, characterized in that the multi-element alloy modified porous metal matrix is prepared by the preparation method according to any one of claims 1 to 8;
the lithium metal negative electrode comprises a porous metal matrix and lithium metal filled in pores of the porous metal matrix;
the holes of the porous metal matrix are modified by a multi-element alloy.
10. A lithium metal battery comprising a lithium metal negative electrode of the multi-element alloy-modified porous metal matrix of claim 9.
CN202310731010.1A 2023-06-20 2023-06-20 Lithium metal negative electrode and preparation method and application thereof Pending CN116613283A (en)

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