CN111370698A - Composite metal material, preparation method and application thereof, high-energy-density battery and symmetrical button battery - Google Patents

Composite metal material, preparation method and application thereof, high-energy-density battery and symmetrical button battery Download PDF

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CN111370698A
CN111370698A CN202010157510.5A CN202010157510A CN111370698A CN 111370698 A CN111370698 A CN 111370698A CN 202010157510 A CN202010157510 A CN 202010157510A CN 111370698 A CN111370698 A CN 111370698A
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metal
battery
electrolyte
metal material
composite metal
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孙春文
易强
杨国鹏
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Beijing Institute of Nanoenergy and Nanosystems
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Beijing Institute of Nanoenergy and Nanosystems
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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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)
  • Secondary Cells (AREA)

Abstract

The invention relates to the field of batteries, and discloses a composite metal material, a preparation method and application thereof, a high-energy-density battery and a symmetrical button battery. The composite metal material includes a first metal phase and a second metal phase; the first metal phase is selected from at least one of lithium, sodium and potassium; the second metal phase is at least one selected from bismuth, antimony, indium, tin and gallium; the content of the first metal phase is 80 to 99 wt% and the content of the second metal phase is 1 to 20 wt% based on the total weight of the anode material. The composite metal material can inhibit the growth of metal dendrites, can be suitable for various electrolyte types when being used for preparing batteries, and the obtained batteries have excellent cycle performance and wide application prospect.

Description

Composite metal material, preparation method and application thereof, high-energy-density battery and symmetrical button battery
Technical Field
The invention relates to the field of batteries, in particular to a composite metal material, a preparation method and application thereof, a high-energy-density battery and a symmetrical button battery.
Background
In recent years, lithium/sodium-metal batteries have received much attention from researchers due to their high energy density. However, the growth of metal dendrites in the cell during cycling severely limits the practical application of such cells. In order to solve the problem of growth of metal dendrites, researchers solve the dendritic growth existing in the metal negative electrode by improving the electrolyte of the battery, modifying the surface of the metal negative electrode, adopting a porous frame containing metal and the like. The growth of metal dendrites is inhibited from the perspective of the electrolyte, primarily by varying the composition and concentration of the electrolyte. Researchers have added small amounts of other components such as fluoroethylene carbonate (FEC), lithium nitrate (LiNO) to liquid electrolytes3) And silicon tetrachloride (SiCl)4) And forming a stable interface layer on the surface of the lithium metal negative electrode to achieve the purpose of inhibiting the growth of metal dendrites. In addition, a surfactant and a metal salt having a lower reduction potential, such as rubidium hexafluorophosphate (RbPF), are added to the electrolyte6) And cesium hexafluorophosphate (CsPF)6) And regulating the cation number on the metal cathode to make the lithium/sodium ions uniformly deposited on the metal cathode so as to achieve the purpose of inhibiting the growth of dendrites. In addition, researchers also add a protective layer with high mechanical strength on the surface of the metal negative electrode to stabilize the metal lithium negative electrode and inhibit the growth of metal dendrites. In addition, by using a porous frame capable of accommodating metal, the metal can be uniformly deposited in the frame, and the growth of metallic lithium dendrites is prevented from causing short circuits in the battery.
Although a protective layer is formed on the surface of the metal negative electrode by adding an additive into the electrolyte, the interface of the metal negative electrode can be stabilized in a short time, and the growth of metal dendrites is inhibited. However, the formation of a protective layer on the metal surface requires continuous consumption of electrolyte and additives, so that dendritic growth also occurs during long-term cycling. Meanwhile, the introduction of additives in the electrolyte can also affect the capacity of the battery. In addition, the methods are mainly applied to combustible carbonate and ether electrolytes, but are rarely reported in phosphate flame-retardant electrolytes.
However, the above method for suppressing the growth of metal dendrites can be used only in carbonate and ether electrolytes, and cannot be applied to other types of electrolytes.
Disclosure of Invention
The invention aims to overcome the problem of limitation of the application field of inhibiting the growth of metal dendrites in the prior art, and provides a composite metal material, a preparation method and application thereof, a high-energy density battery and a symmetrical button battery.
In order to achieve the above object, a first aspect of the present invention provides a composite metal material, wherein the composite metal material includes a first metal phase and a second metal phase;
the first metal phase is selected from at least one of lithium, sodium and potassium;
the second metal phase is selected from at least one of bismuth, antimony, indium, tin and gallium.
The content of the alkali metal is 80 to 99 wt% and the active metal component is 1 to 20 wt%, based on the total weight of the composite metal material.
In a second aspect, the present invention provides a method of preparing the composite metal material of the present invention, wherein the method comprises the steps of:
and mixing the first metal phase and the second metal phase in an inert atmosphere, and forming to obtain the composite metal material.
In a third aspect, the invention provides a use of the composite metal material of the invention in a battery.
A fourth aspect of the invention provides a high energy density battery, wherein the battery comprises a battery positive electrode, a battery negative electrode and an electrolyte;
the battery cathode is made of the composite metal material;
the electrolyte is selected from at least one of carbonate electrolyte, ether electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
A fifth aspect of the invention provides a symmetric button cell battery, wherein the battery comprises a metal electrode and an electrolyte;
the metal electrode is the composite metal material;
the electrolyte is selected from at least one of carbonate electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
Through the technical scheme, the composite metal material, the preparation method and the application thereof, the high-energy density battery and the symmetrical button battery provided by the invention have the following beneficial effects:
in the composite metal material provided by the invention, the second metal phase is added into the alkali metal as the first metal phase, so that the surface tension and the affinity to lithium/sodium ions of the metal composite material are obviously improved, and the deposition form of the lithium/sodium ions on the metal surface is regulated and controlled, thereby achieving the purpose of inhibiting the growth of metal dendrites.
The composite metal material provided by the invention can be used as an electrode material not only in carbonate and ether electrolytes, but also in flame-retardant phosphate electrolytes and other liquid and gel electrolytes. And the sodium/lithium-metal battery assembled by the composite metal electrode is expected to have excellent cycle performance and wide application prospect.
Drawings
FIG. 1(a) is a graph of the cycling performance of the cell provided in example 1 at a current density of 0.5 milliamp/cm and a capacity of 0.5 milliamp-hours/cm;
FIG. 1(b) is a graph of the cycling performance of the cell provided in example 2 at a current density of 0.5 milliamp/cm and a capacity of 0.5 milliamp-hours/cm;
FIG. 2 is a graph of the cycling performance of the cell provided in comparative example 1 at a current density of 0.5 milliamp/cm and a capacity of 0.5 milliamp-hours/cm;
FIG. 3(a) is a graph of the cycling performance of the cell provided in example 3 at a current density of 1 milliamp/cm and a capacity of 1 milliamp-hour/cm;
FIG. 3(b) is a graph of the cycling performance of the cell provided in example 4 at a current density of 1 milliamp/cm and a capacity of 1 milliamp-hour/cm;
FIG. 3(c) is a graph of the cycling performance of the cell provided in example 5 at a current density of 1 milliamp/cm and a capacity of 1 milliamp-hour/cm;
FIG. 4 is a graph of the cycling performance of the cell provided in comparative example 2 at a current density of 1 milliamp/cm and a capacity of 1 milliamp-hour/cm;
FIG. 5 is a graph of the cycling performance of the battery provided in example 8;
fig. 6 is a graph of the cycle performance of the battery provided in comparative example 4;
FIGS. 7a and 7b are scanning electron micrographs of the sodium metal surface of a sodium metal symmetric cell after 100 hours of cycling at different magnifications, respectively, with a current density of 1 mA/cm and a capacity of 1 mA/cm;
fig. 7c and 7d are scanning electron micrographs of the bismuth-sodium metal surface after 100 hours of cycling of the symmetric cell with the bismuth-sodium composite metal material negative electrode at different magnifications, respectively, with a current density of 1 milliamp/square centimeter and a capacity of 1 milliamp-hour/square centimeter.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
A first aspect of the present invention provides a composite metal material, wherein the composite metal material comprises a first metal phase and a second metal phase;
the first metal phase is selected from at least one of lithium, sodium and potassium;
the second metal phase is at least one selected from bismuth, antimony, indium, tin and gallium;
the content of the first metal phase is 80 to 99 wt% and the second metal phase contains 1 to 20 wt% of phosphorus, based on the total weight of the composite metal material.
In the invention, the second metal phase is added into the alkali metal as the first metal phase, so that the surface tension and the affinity to lithium/sodium ions of the metal composite material are obviously improved, and the deposition form of the lithium/sodium ions on the surface of the metal composite material is regulated and controlled, thereby achieving the purpose of inhibiting the growth of metal dendrites.
Specifically, the inventors of the present invention have studied and found that when the content of the first metal phase is 80 to 99 wt% and the content of the second metal phase is 1 to 20 wt% based on the total weight of the metal composite, the obtained metal composite has better mechanical strength, plasticity and oxidation resistance, and the battery assembled from the same as an electrode material has more excellent cycle performance.
Further, when the content of the first metal phase is 88 to 92 wt% and the content of the second metal phase is 8 to 12 wt% based on the total weight of the metal composite, the obtained metal composite has more excellent properties.
Further, when the content of the first metal phase is 90 wt% and the content of the second metal phase is 10 wt% based on the total weight of the metal composite, the obtained metal composite has more excellent properties.
According to the invention, the first metal phase is selected from lithium and/or sodium. More preferably, the first metal phase is sodium.
According to the invention, the first metal phase is selected from at least one of bismuth, antimony, indium, tin and gallium.
In a second aspect, the present invention provides a method of preparing the composite metal material of the present invention, wherein the method comprises the steps of:
and mixing the first metal phase and the second metal phase in an inert atmosphere, and forming to obtain the composite metal composite material.
According to the invention, the composite metal material is prepared in an inert atmosphere, so that the influence of impurities and the like in the external environment on the performance of the composite metal material in a battery can be avoided.
In the invention, the first metal phase and the second metal phase are mixed to obtain a metal mixture.
According to the invention, the mixing is carried out by means of a mechanical mixing and/or melt mixing.
According to the invention, the shaping is selected from forging and/or stamping.
In a third aspect, the invention provides a use of the composite metal material of the invention in a battery.
According to the invention, the battery is a lithium ion battery or a sodium ion battery.
A fourth aspect of the invention provides a high energy density battery, wherein the battery comprises a battery positive electrode, a battery negative electrode and an electrolyte;
the battery cathode is made of the composite metal material;
the electrolyte is selected from at least one of carbonate electrolyte, ether electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
In the present invention, the carbonate electrolyte is prepared by dissolving corresponding sodium salt (such as NaPF) in one or more organic carbonate solvents6) Is prepared. The carbonate-based organic solvent is at least one selected from dimethyl carbonate (DMC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), and diethyl carbonate (DEC).
In the present invention, the ether electrolyte is prepared by dissolving corresponding sodium salt (such as NaPF) in ether organic solvent6) Is prepared. The ether organic solvent is selected from ethylene glycol dimethyl ether (DME) and diethylene glycol Dimethyl Ether (DEGD)ME) and triethylene glycol dimethyl ether (TEGDME).
In the present invention, the phosphate electrolyte is a sodium salt (e.g., NaPF) corresponding to a phosphate organic solvent6) Is prepared. The phosphate organic solvent is at least one selected from trimethyl phosphate (TMP), triethyl phosphate (TEP) and trimethyl methyl phosphate (DMMP).
A fifth aspect of the invention provides a symmetric button cell battery, wherein the battery comprises a metal electrode and an electrolyte;
the metal electrode is the composite metal material;
the electrolyte is selected from at least one of carbonate electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
The electrolyte is as described above and will not be described in detail here.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
preparation example 1
In an argon-filled glove box, a button cell (R2032) for a symmetrical battery is assembled by taking a composite metal electrode material as a metal electrode and an electrolyte of the battery, the electrolyte is a flame-retardant phosphate electrolyte which is TMP and FEC, wherein the volume content of FEC is 5%, and 1 mol of NaPF is dissolved in the electrolyte6The amount of electrolyte used was 50 ml.
Preparation example 2
The battery anode slurry is composed of 80% of Na by mass3V2(PO4)3Mixing 15% acetylene black and 5% polyvinylidene fluoride (PVDF), coating the slurry on Al foil, drying at 120 deg.C for 12 hr in vacuum, cutting into electrode sheets, and weighing for use. Wherein the loading of the active material of the positive electrode material is 5.5 mg/square centimeter. The battery cathode is made of a composite metal material, the electrolyte is a flame-retardant phosphate electrolyte which is TMP and FEC, wherein the volume content of FEC is 5%, and 1 mol of NaPF is dissolved in the electrolyte6The amount of the electrolyte was 50 ml.
Electrochemical performance test
The cycling performance of the batteries was tested in a battery tester (LAND CT 2001A).
The appearance of the electrode made of the composite metal material after circulation is characterized by Scanning Electron Microscopy (SEM).
The raw materials used in the examples and comparative examples are all commercially available products.
Example 1
Preparing a composite metal material: adding bismuth Bi into powder of alkali metal Na in nitrogen atmosphere, and mechanically mixing uniformly to obtain the composite metal. Then, the composite metal material electrode sheet A1 with the diameter of 10 mm and the thickness of 200 microns is obtained by casting. Wherein the Na content is 90 wt%, and the Bi content is 10 wt%.
A battery was assembled as in preparation example 1, wherein an electrolyte carbonate electrolyte, in which the carbonate electrolyte was EMC and DMC in a volume ratio of 6:4, was dissolved with 1 mole of NaPF6The cycle performance of the cell at a current density of 0.5 milliamp/cm and a capacity of 0.5 milliamp-hour/cm is shown in fig. 1 (a). As can be seen from fig. 1(a), the symmetric cell exhibits a stable and small overpotential after the first few cycles and can continue to stabilize the cycle. Showing that the sodium ions can be reversibly deposited and peeled on the surface of the composite metal material as the negative electrode.
Example 2
Preparing a composite metal material: in a nitrogen atmosphere, indium In was added to an alkali metal Na powder, and the mixture was mechanically mixed uniformly to obtain a composite metal. Then, the composite metal material electrode sheet A2 with the diameter of 10 mm and the thickness of 200 microns is obtained by casting. Wherein the Na content is 90 wt%, and the In content is 10 wt%.
A battery, in which a carbonate-based electrolyte was used as an electrolyte, was assembled according to preparation example 1, and the cycle performance at a current density of 0.5 ma/cm and a capacity of 0.5 ma-hr/cm was shown in fig. 1 (b). As can be seen from fig. 1(b), the symmetric cell exhibits a stable and small overpotential after the first few cycles and can continue to stabilize the cycle. Showing that the sodium ions can be reversibly deposited and peeled on the surface of the composite metal material as the negative electrode.
Example 3
A battery was assembled according to the method of example 1, except that: the electrolyte is phosphate ester liquid electrolyte. The cycle performance of the cell at a current density of 1 ma/cm and a capacity of 1 ma-hr/cm is shown in fig. 3 (a). As can be seen from fig. 3(a), the composite metal material as the battery negative electrode also has excellent cycle stability in the flame-retardant phosphate electrolyte.
Example 4
A battery was assembled according to the method of example 2, except that: the electrolyte is phosphate ester liquid electrolyte. The cycle performance of the cell at a current density of 1 ma/cm and a capacity of 1 ma-hr/cm is shown in fig. 3 (b). As can be seen from fig. 3(b), the composite metal material as the battery negative electrode also has excellent cycle stability in the flame-retardant phosphate electrolyte.
Example 5
Preparing a composite metal material: adding bismuth Sb into powder of alkali metal Na in nitrogen atmosphere, and mechanically and uniformly mixing to obtain the composite metal. Then, the composite metal material electrode sheet A2 with the diameter of 10 mm and the thickness of 200 microns is obtained by casting. Wherein the Na content is 90 wt%, and the In content is 10 wt%.
A battery was assembled according to preparation example 1, in which the electrolyte was a phosphate-based liquid electrolyte, and the cycle performance of the battery at a current density of 1 ma/cm and a capacity of 1 ma-hr/cm was shown in fig. 3 (c). As can be seen from fig. 3(c), the composite metal material as the battery negative electrode also has excellent cycle stability in the flame-retardant phosphate electrolyte.
Example 6
A battery was assembled according to the method of example 1, except that: the Na content was 85 wt%, and the Bi content was 15 wt%. The cell was short-circuited after 100 hours of cycling.
Example 7
A battery was assembled according to the method of example 1, except that: and simultaneously adding bismuth Bi and indium In into the powder of the alkali metal Na to prepare the composite metal material electrode sheet A7. Wherein the Na content is 90 wt%, and the Bi content is 5 wt%; the In content was 5 wt%. The cell can be stably cycled for over 200 hours.
Comparative example 1
A battery was assembled as in example 1, except that pure Na metal was used as the negative electrode for the battery. The cycle performance of the resulting cell at a current density of 0.5 milliamp/cm and a capacity of 0.5 milliamp-hours/cm is shown in fig. 2. As can be seen from fig. 2, after 117 hours of cycling, the cell developed a short circuit, meaning the growth of dendrites in the cell.
Comparative example 2
A battery was assembled according to the method of example 3, except that: pure Na metal is used as a negative electrode of the battery. The cycle performance of the resulting cell at a current density of 1 ma/cm and a capacity of 1 ma-hr/cm is shown in fig. 4. As can be seen from fig. 4, after 39 hours of cycling, the cell developed a short circuit, meaning the growth of dendrites in the cell.
Comparative example 3
A battery was assembled according to the method of example 1, except that: the Na content was 70 wt%, and the Bi content was 30 wt%. The cell can only be cycled stably for 80 hours.
Example 8
A battery was assembled in accordance with preparation example 2, wherein the Bi-Na composite metal material obtained in example 1 was used as a negative electrode, Na3V2(PO4)3And (3) adopting phosphate electrolyte as a positive electrode to assemble to obtain the sodium ion battery. The cycle performance of the cell at 1C current density (corresponding to 117 milliamps/gram) is shown in fig. 5.
As can be seen from fig. 5, the anode provided by the present invention has excellent cycle stability in the assembled battery.
Comparative example 4
A battery was assembled according to the method of example 8, except that: pure Na metal is used as a negative electrode. Cycling performance plot of the resulting cell at 1C (corresponding to 117 milliamps/gram) current density. As can be seen from fig. 6, after 91 cycles, a short circuit was generated inside the battery, resulting in the failure of the battery.
As shown in fig. 7, in which, fig. 7a and 7b are scanning electron micrographs of the sodium metal surface of the sodium symmetric battery after 100 hours of circulation under different magnifications, respectively, when the current density is 1 ma/cm and the capacity is 1 ma-hr/cm; fig. 7c and 7d are scanning electron micrographs of the bismuth-sodium metal surface after 100 hours of cycling of the symmetric cell with the bismuth-sodium composite metal negative electrode at a current density of 1 milliampere per square centimeter and a capacity of 1 milliampere per square centimeter, respectively, at different magnifications.
As can be seen from fig. 7, the surface of the composite metal was more flat after 100 hours of cycling for the cell with the bismuth-sodium composite metal as the negative electrode, indicating that sodium ions were deposited more uniformly on the surface of the composite metal negative electrode, relative to the cell with sodium metal as the negative electrode.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A composite metal material, wherein the composite metal material comprises a first metal phase and a second metal phase;
the first metal phase is selected from at least one of lithium, sodium and potassium;
the second metal phase is at least one selected from bismuth, antimony, indium, tin and gallium;
the content of the first metal phase is 80 to 99 wt% and the content of the second metal phase is 1 to 20 wt% based on the total weight of the anode material.
2. The composite metal material according to claim 1, wherein the content of the first metal phase is 88-92 wt% and the content of the second metal phase is 8-12 wt%, based on the total weight of the composite metal material.
3. The composite metal material according to claim 1 or 2, wherein the first metal phase is selected from lithium and/or sodium;
preferably, the second metal phase is selected from at least one of bismuth, antimony and indium.
4. A method of making the composite metal material of any one of claims 1 to 3, wherein the method comprises the steps of:
and mixing the first metal phase and the second metal phase in an inert atmosphere, and forming to obtain the composite metal material.
5. The method of claim 4, wherein the mixing is selected from mechanical mixing and/or melt mixing.
6. The method of claim 4 or 5, wherein the forming is selected from forging and/or stamping.
7. Use of a composite metal material according to any one of claims 1 to 3 in a battery.
8. The use according to claim 7, the battery being a lithium ion battery or a sodium ion battery.
9. A high energy density battery, wherein the battery comprises a battery positive electrode, a battery negative electrode, and an electrolyte;
the battery negative electrode is the composite metal material of any one of claims 1 to 3;
the electrolyte is selected from at least one of carbonate electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
10. A symmetric button cell, wherein the cell comprises a metal electrode and an electrolyte;
the metal electrode is the composite metal material of any one of claims 1 to 3;
the electrolyte is selected from at least one of carbonate electrolyte, phosphate electrolyte, gel electrolyte and solid electrolyte.
CN202010157510.5A 2020-03-09 2020-03-09 Composite metal material, preparation method and application thereof, high-energy-density battery and symmetrical button battery Pending CN111370698A (en)

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CN106784629A (en) * 2017-01-19 2017-05-31 武汉大学 A kind of lithium metal battery cathode interface method of modifying
CN110120502A (en) * 2018-02-05 2019-08-13 中国科学院物理研究所 A kind of lithium metal alloy material of cathode and its preparation method and application
CN110783529A (en) * 2018-07-31 2020-02-11 中南大学 Lithium metal cathode for secondary battery and preparation and application thereof

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