CN115528213A - Lithium metal composite negative electrode material and preparation method thereof - Google Patents

Lithium metal composite negative electrode material and preparation method thereof Download PDF

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CN115528213A
CN115528213A CN202211343463.9A CN202211343463A CN115528213A CN 115528213 A CN115528213 A CN 115528213A CN 202211343463 A CN202211343463 A CN 202211343463A CN 115528213 A CN115528213 A CN 115528213A
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lithium
carbon fiber
negative electrode
fiber cloth
lithium metal
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CN115528213B (en
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孙福根
叶承舟
江伟伟
张婧
黄龙
邹涵韬
李俊杰
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Nanchang 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
    • H01M4/13—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
    • 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
    • H01M4/13—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
    • H01M4/36—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
    • H01M4/382—Lithium
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
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    • 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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Abstract

The invention belongs to the technical field of lithium metal batteries, and particularly discloses a lithium metal composite negative electrode material and a preparation method thereof. The lithium metal composite negative electrode material is obtained by growing a silver compound on carbon fiber cloth in situ by a hydrothermal method and then soaking the carbon fiber cloth in molten metal lithium. The invention converts the lithium-phobic carbon fiber cloth into the lithium-philic three-dimensional porous skeleton Ag-X @ CFC by coating a uniform silver compound Ag-X layer on the surface of the carbon cloth fiber. In addition, in the lithiation process, the Ag-X coating layer can be converted into high-conductivity lithium-philic Ag and a lithium compound Li-X conducted by lithium ions, so that not only can uniform and rich lithium nucleation active sites be provided, but also a three-dimensional skeleton network structure with cross conduction of electrons and lithium ions can be formed in the lithium metal composite negative electrode, the growth of negative electrode lithium dendrites is inhibited efficiently for a long time, the uniform deposition of the lithium metal is obviously promoted, and the long-term cycle performance of the lithium metal negative electrode is greatly improved.

Description

Lithium metal composite negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a lithium metal composite negative electrode material and a preparation method thereof.
Background
In recent years, with the vigorous development of various smart devices, electric vehicles, and the like, secondary battery energy storage systems typified by lithium ion batteries have been widely used. However, it is increasingly difficult for commercial lithium ion batteries to meet their requirements in terms of energy density, cycle stability, and safety. In order to effectively improve the energy density of the battery, a high-capacity negative electrode material is developed to replace the graphite negative electrode material (372 mAh g) which has the highest commercial degree but low theoretical specific capacity -1 ) Is one of effective solution ideas. Therefore, the development of a new generation of high energy density lithium ion battery cathode material is also a major concern in the current academic and industrial fields.
Among the many negative electrode material candidates for lithium ion batteries, the lithium metal negative electrode has a very high theoretical specific capacity (3860 mAh g) -1 ) Lowest working potential (-3.04V vs H) + /H 2 ) And a lower density (0.534 g cm) -3 ) The "holy cup" negative electrode, known as a lithium secondary battery, has received considerable attention from researchers. However, the current application of lithium metal anodes presents several significant drawbacks: (1) The electrodeposition process of the lithium metal of the negative electrode is inclined to generate dendritic lithium thermodynamically, and meanwhile, the uneven distribution of the surface electric field of the dendritic lithium promotes the uneven deposition of lithium ions and the disordered growth of lithium dendrites; (2) The growth of a large amount of lithium dendrites is easy to pierce a diaphragm, so that the internal short circuit and safety problems of the battery are caused; (3) The uneven dissolution of lithium dendrites generates a large amount of 'dead lithium' separated from the negative electrode, so that the metal lithium negative electrode is pulverized; (4) The above huge volume change of the lithium negative electrode makes the SEI film unable to stably cover the surface thereof, resulting in the continuous formation of the SEI film, the continuous depletion of the electrolyte, and the reduction of the coulombic efficiency and the cycle life of the battery. These problems greatly limit the commercial application of lithium metal negative electrodes.
In order to solve the problems of the current lithium metal negative electrode, researchers at home and abroad adopt strategies such as electrolyte modification, artificial SEI film construction and the like to improve the interface stability of the metal lithium, but the methods cannot fundamentally solve the problems of huge volume strain, lithium dendrite growth and battery failure of the lithium metal negative electrode. In the current research field, the construction of a three-dimensional porous skeleton (such as metal foams of copper, nickel and the like, carbon cloth, carbon nanotubes, graphene films and the like) for a lithium metal negative electrode is considered to be an effective scheme for accommodating electrode volume strain and inhibiting lithium dendrite growth. According to the Sand model, the high specific surface area of the three-dimensional framework material can reduce the local current density of lithium ion deposition and delay the starting time of lithium dendrite generation. Meanwhile, the three-dimensional porous structure of the framework material can accommodate the volume strain of the lithium negative electrode, so that the interface stability of the lithium metal negative electrode is improved. The three-dimensional carbon fiber cloth is regarded as a lithium negative electrode framework material with high application value due to the characteristics of light weight, ultrahigh conductivity, interface modifiability, low cost, easy commercial availability and the like. However, the lithium-phobicity of the carbon material interface increases the nucleation overpotential and the deposition resistance of the metallic lithium on the surface thereof. Particularly, at a higher current density, lithium nucleation sites on the lithium-phobic surface are easy to be distributed in an isolated manner, and subsequent lithium ions are more prone to be preferentially deposited on the nucleation sites, so that lithium metal is unevenly deposited in a porous lithium-phobic carbon cloth fiber framework, and the problem of dendritic growth of lithium on a negative electrode after long-time circulation is inevitable. Therefore, the three-dimensional porous carbon cloth fiber skeleton needs to be modified by lithium affinity to inhibit the growth of lithium dendrites of the negative electrode, and finally the long-term cycle performance of the lithium metal negative electrode is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a lithium metal composite negative electrode material and a preparation method thereof, and the following technical scheme is adopted specifically:
a preparation method of a lithium metal composite negative electrode material comprises the following steps:
growing a silver compound on the carbon fiber cloth in situ by a hydrothermal method to obtain the carbon fiber cloth coated by the silver compound;
and secondly, immersing the carbon fiber cloth coated with the silver compound into molten metal lithium, and quickly filling the molten metal lithium into the carbon fiber cloth coated with the silver compound to obtain the lithium metal composite negative electrode material.
Wherein the silver compound is Ag-X, and X is at least one of O, S, se, P, F and I.
In the lithium metal composite negative electrode material prepared by the invention, the carbon fiber cloth framework in the lithium metal composite negative electrode is coated with the silver compound Ag-X, and the silver compound Ag-X can be converted into the high-conductivity lithium-philic Ag and the lithium compound Li-X which is conducted by lithium ions in the lithiation process, so that a three-dimensional framework network structure with cross conduction of electrons and lithium ions is formed in the lithium metal composite negative electrode, and the growth of negative electrode lithium dendrites can be inhibited efficiently for a long time.
In the preparation method, the specific process of the first step is as follows: mixing the carbon fiber cloth with the coating precursor solution for hydrothermal reaction, so that a silver compound grows on the carbon fiber cloth in situ to obtain the carbon fiber cloth coated with the silver compound; the coating precursor solution comprises AgNO 3 . Preferably, the coating precursor solution further comprises a sulfur-containing compound (e.g., na) 2 S), selenium-containing compound (such as NaSeO) 3 ) Phosphorus-containing compounds (e.g. Na) 2 HPO 2 ) Fluorine-containing compounds (e.g. NH) 4 F) And iodine-containing compounds (e.g., naI O) 3 ) At least one of (1).
In the preparation method, the hydrothermal reaction conditions of the first step comprise: the temperature is 180-220 ℃, and the time is 600-800 min. Preferably, after the silver compound grows on the carbon fiber cloth in situ, deionized water and absolute ethyl alcohol are adopted for cleaning, and the carbon fiber cloth coated with the silver compound is obtained after drying.
Preferably, the preparation method further comprises a pretreatment step before the step one, and the specific process is as follows: and sequentially putting the carbon fiber cloth into an acetone and nitric acid solution, ultrasonically degreasing, washing with deionized water and absolute ethyl alcohol, and drying to obtain the purified carbon fiber cloth. Preferably, the time for ultrasonic degreasing is 10min-20min.
The invention has the beneficial effects that: the invention uses simple in-situ growth method to coat a layer of even silver compound Ag-X layer on the surface of the carbon cloth fiber, and the carbon cloth with lithium-phobicity is converted into the three-dimensional porous skeleton Ag-X @ CFC with lithium-philic property. In addition, in the lithiation process, the Ag-X coating layer can be converted into high-conductivity lithium-philic Ag and a lithium compound Li-X conducted by lithium ions, so that uniform and rich lithium nucleation active sites can be provided, and a three-dimensional framework network structure with cross conduction of electrons and lithium ions can be formed in the lithium metal composite negative electrode, so that the growth of lithium dendrites of the negative electrode is inhibited efficiently for a long time, the uniform deposition of the lithium metal is obviously promoted, and the long-term cycle performance of the lithium metal negative electrode is greatly improved.
Drawings
FIG. 1 shows a SEM image of a Carbon Fiber Cloth (CFC);
FIG. 2 shows a cloth of silver selenide coated carbon fiber (Ag) prepared in example 1 2 Se @ CFC);
FIG. 3 shows Ag selenide coated carbon fiber cloth (Ag) obtained in example 1 2 Se @ CFC) and Li | | | Ag of copper foil (Cu foil) 2 Coulomb efficiency comparison graph of Se @ CFC and Li | | | Cu foil asymmetric battery (current density 1mA/cm 2 Circulation capacity of 1mA/cm 2 )；
FIG. 4 shows Ag obtained in example 1 2 Comparative cycle performance diagram (current density 1 mA/cm) of symmetric battery with Se @ CFC/Li and pure metal Li cathode 2 Circulation capacity of 1mA/cm 2 )；
FIG. 5 shows Ag obtained in example 1 2 Rate performance plot for symmetric cells of Se @ CFC/Li (current densities 0.5, 1, 3, 5 mA/cm) 2 Circulation capacity of 1mA/cm 2 )；
FIG. 6 shows the heterogeneous Ag obtained in example 2 2 SEM picture of Se @ CFC;
FIG. 7 shows Ag obtained in example 3 2 Cycle performance diagram (Current Density 1 mA/cm) of S @ CFC/Li symmetrical cell 2 Circulation capacity of 1mA/cm 2 )；
FIG. 8 shows the heterogeneous Ag films obtained in example 4 2 SEM picture of Se @ CFC;
FIG. 9 shows the nonuniformity obtained in example 5Ag 2 SEM picture of Se @ CFC;
FIG. 10 shows the heterogeneous Ag films obtained in example 6 2 SEM picture of Se @ CFC;
FIG. 11 is a graph showing the cycle performance of the symmetric cell made in example 7 with Ag @ CFC/Li (current density 1 mA/cm) 2 Circulation capacity of 1mA/cm 2 )。
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
Example 1:
a preparation method of a lithium metal composite negative electrode material comprises the following steps:
(1) Cutting a carbon fiber cloth substrate material into a wafer with the diameter of 16mm, respectively putting the wafer into 50mL of acetone and concentrated nitric acid (8 mol/L) solution, ultrasonically degreasing for 20min, respectively cleaning with deionized water and absolute ethyl alcohol, and drying;
(2) Placing the cleaned carbon fiber cloth CFC (shown as SEM image of CFC in figure 1) in 0.05mol/L ammonia water mixed solution of silver nitrate and elemental selenium, adding into a high-pressure reaction kettle, performing hydrothermal reaction at 200 ℃ for 720min, taking out, cleaning with deionized water and absolute ethyl alcohol, and drying in an air-blast drying oven to obtain the silver selenide coated carbon fiber cloth Ag 2 Se @ CFC (shown in FIG. 2 as Ag) 2 SEM image of Se @ CFC, it can be seen from FIG. 2 that the surface of carbon cloth fiber is coated with Ag 2 Uniform and complete Se coating);
(3) In a glove box with the water oxygen value less than 0.5ppm, firstly, heating a metal lithium sheet to a molten state, and then, carrying out the step (2) to obtain Ag 2 Immersing Se @ CFC sheet in liquid lithium metal to quickly fill Ag with molten lithium 2 Se @ CFC, taking out, naturally cooling to obtain Ag 2 Se @ CFC/Li metal composite cathode.
The Ag obtained in the last step 2 Se @ CFC/Li metal composite negative electrode is made into asymmetric half cell, symmetric half cell and full cell in glove box, and charge-discharge cycle test result shows that Ag 2 Se@CFC/The Li composite negative electrode has excellent cycle stability.
FIG. 3 shows a cloth made of silver selenide coated carbon fiber (Ag) 2 Se @ CFC) and Li | | | Ag of copper foil (Cu foil) 2 Coulombic efficiency comparison plots for se @ cfc versus Li | | Cu foil asymmetric cells. As can be seen from FIG. 3, li | | | Ag 2 The Se @ CFC asymmetric battery has ultrahigh coulombic efficiency, and can still maintain 99.1% after the lithium metal is cyclically deposited/extracted for 250 times. FIG. 4 shows Ag 2 Comparative cycling performance plots for symmetric cells with Se @ CFC/Li and pure metal Li cathodes. As can be seen from FIG. 4, ag 2 The symmetric half-cell with Se @ CFC/Li composite cathode has extremely low lithium deposition overpotential and ultrahigh cycle performance, and the current density is 1mA/cm 2 And a circulation capacity of 1mAh/cm 2 Under the condition, the overpotential of lithium deposition after 1200h (600 times) of circulation is still lower than 5mV. FIG. 5 shows Ag 2 Rate performance plot for symmetric cell of Se @ CFC/Li. It can be seen that Ag 2 After the symmetrical half-cell of the Se @ CFC/Li composite cathode is subjected to charge-discharge cycles with different current densities, the extremely high cycle stability and the extremely low lithium deposition overpotential are still maintained.
Example 2:
the difference from example 1 is: cutting a carbon fiber cloth substrate material into round pieces with the diameter of 16mm, respectively putting the round pieces into 50mL of acetone solution, ultrasonically degreasing for 20min, respectively cleaning with deionized water and absolute ethyl alcohol, and drying; the rest is the same as in example 1.
Prepared Ag 2 Ag on Se @ CFC surface 2 Non-uniformity of Se coating layer indicates that Ag is pretreated by concentrated nitric acid 2 The Se coating effect has a large impact (as shown in fig. 6).
Example 3:
the difference from example 1 is: step (2) placing the cleaned carbon fiber cloth CFC in Na 2 S·9H 2 Of O with PVP [ Ag (NH) 3 ) 2 ]The OH mixed solution was subjected to hydrothermal reaction at 160 ℃ in a high-pressure reactor for 600min and then taken out, and the procedure was repeated as in example 1.
The prepared silver sulfide coated carbon fiber cloth/lithium metal composite negative electrode (Ag) 2 Cyclability of S @ CFC/Li)Can be better than pure Li metal cathode, but is inferior to Ag 2 Se @ CFC/Li composite cathode, illustrating Ag 2 Formation of Li in the S cladding layer during lithiation 2 S has some effect on the electrochemical performance of the lithium metal negative electrode (as shown in fig. 7).
Example 4:
the difference from example 1 is: and (2) placing the cleaned carbon fiber cloth CFC in 0.02mol/L ammonia water mixed solution of silver nitrate and elemental selenium, wherein the rest is the same as the embodiment 1.
Prepared Ag 2 Ag on Se @ CFC surface 2 The Se coating is not uniform, which shows that the concentration of silver nitrate has great influence on the coating effect of silver selenide (as shown in figure 8).
Example 5:
the difference from example 1 is: and (2) placing the cleaned carbon fiber cloth CFC in 0.05mol/L ammonia water mixed solution of silver nitrate and elemental selenium, reacting for 720min at the temperature of 160 ℃ in a high-pressure reaction kettle, and taking out, wherein the rest is the same as in the embodiment 1.
Prepared Ag 2 Ag on Se @ CFC surface 2 The non-uniformity of the Se coating layer shows that the hydrothermal reaction temperature has a great influence on the coating effect of the silver selenide (as shown in figure 9).
Example 6:
the difference from example 1 is: and (2) placing the cleaned carbon fiber cloth CFC in 0.05mol/L ammonia water mixed solution of silver nitrate and elemental selenium, reacting in a high-pressure reaction kettle at the temperature of 200 ℃ for 360min, and taking out, wherein the rest is the same as in the embodiment 1.
Prepared Ag 2 Ag on Se @ CFC surface 2 The Se coating layer is not uniform, which shows that the hydrothermal reaction time has great influence on the coating effect of the silver selenide (as shown in figure 10).
Example 7:
the difference from example 1 is: and (2) putting the cleaned carbon fiber cloth CFC into 0.05mol/L silver nitrate and PVP aqueous solution, evaporating water, putting into a tubular furnace in a nitrogen atmosphere, and carrying out heat treatment at the temperature of 400 ℃ for 3 hours to obtain silver-coated carbon fiber cloth Ag @ CFC, wherein the rest is the same as that in the embodiment 1.
The prepared silver-coated carbon fiber cloth/lithium metal composite negative electrode (Ag @ CFC/Li) has better cycle performance than that of a pure Li metal negative electrode, but is inferior to that of Ag 2 Se @ CFC/Li composite cathode, illustrating Ag 2 High-conductivity lithium-philic Ag formed by conversion of Se coating layer in lithiation process and high-lithium ion-conductivity Li 2 Se can provide uniform and rich lithium nucleation active sites, and a three-dimensional skeleton network structure with cross conduction of electrons and lithium ions can be formed in the lithium metal composite negative electrode, so that the growth of lithium dendrites of the negative electrode is inhibited efficiently for a long time, the uniform deposition of lithium metal is obviously promoted, and the long-term cycle performance of the lithium metal negative electrode is greatly improved (as shown in figure 11).
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment, and the present invention shall fall within the protection scope of the present invention as long as the technical effects of the present invention are achieved by the same means. The invention is capable of other modifications and variations in its technical solution and/or its implementation, within the scope of protection of the invention.

Claims (10)

1. The preparation method of the lithium metal composite negative electrode material is characterized by comprising the following steps of:
growing a silver compound on the carbon fiber cloth in situ by a hydrothermal method to obtain the carbon fiber cloth coated by the silver compound;
and secondly, immersing the carbon fiber cloth coated with the silver compound into molten metal lithium, and quickly filling the molten metal lithium into the carbon fiber cloth coated with the silver compound to obtain the lithium metal composite negative electrode material.
2. The method of claim 1, wherein the silver compound is Ag-X, and X is at least one of O, S, S e, P, F, and I.
3. The preparation method according to claim 1, wherein the specific process of the first step is as follows: mixing the carbon fiber cloth and the coating precursor solution for hydrothermal reaction to ensure thatGrowing the silver compound on the carbon fiber cloth in situ to obtain the carbon fiber cloth coated by the silver compound; the coating precursor solution comprises AgNO 3 。
4. The method of claim 3, wherein the coating precursor solution further comprises at least one of a sulfur-containing compound, a selenium-containing compound, a phosphorous-containing compound, a fluorine-containing compound, and an iodine-containing compound.
5. The method according to claim 3, wherein the hydrothermal reaction conditions include: the temperature is 180-220 ℃, and the time is 600-800 min.
6. The preparation method according to claim 3, wherein after the silver compound grows on the carbon fiber cloth in situ, the carbon fiber cloth is further cleaned by deionized water and absolute ethyl alcohol and dried to obtain the carbon fiber cloth coated with the silver compound.
7. The preparation method according to claim 1, further comprising a pretreatment step before the first step, wherein the pretreatment step comprises the following specific steps: and sequentially putting the carbon fiber cloth into an acetone and nitric acid solution, ultrasonically degreasing, washing with deionized water and absolute ethyl alcohol, and drying to obtain the purified carbon fiber cloth.
8. The method according to claim 7, wherein the time for ultrasonic degreasing is 10min to 20min.
9. A lithium metal composite negative electrode material characterized by being produced by the production method according to any one of claims 1 to 8.
10. A lithium metal battery comprising a negative electrode made of the lithium metal composite negative electrode material according to claim 9.
CN202211343463.9A 2022-10-31 2022-10-31 Lithium metal composite anode material and preparation method thereof Active CN115528213B (en)

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Publication number Priority date Publication date Assignee Title
CN108365200A (en) * 2018-02-11 2018-08-03 清华大学 A kind of preparation method of compound lithium an- ode
CN109950113A (en) * 2019-03-26 2019-06-28 东华大学 A kind of preparation method and application for the silver-colored silver selenide flexible Field Emission cathode material of richness being grown on carbon cloth
CN113540453A (en) * 2020-08-27 2021-10-22 中南大学 Internal lithium-philic multi-confinement/induction hollow carbon composite framework of lithium metal cathode and preparation method thereof
WO2022000292A1 (en) * 2020-06-30 2022-01-06 宁德时代新能源科技股份有限公司 Composite lithium metal negative electrode, preparation method therefor, and secondary lithium battery and device
CN115117303A (en) * 2021-03-18 2022-09-27 恒大新能源技术(深圳)有限公司 Lithium metal negative electrode, preparation method thereof and lithium secondary battery

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CN108365200A (en) * 2018-02-11 2018-08-03 清华大学 A kind of preparation method of compound lithium an- ode
CN109950113A (en) * 2019-03-26 2019-06-28 东华大学 A kind of preparation method and application for the silver-colored silver selenide flexible Field Emission cathode material of richness being grown on carbon cloth
WO2022000292A1 (en) * 2020-06-30 2022-01-06 宁德时代新能源科技股份有限公司 Composite lithium metal negative electrode, preparation method therefor, and secondary lithium battery and device
CN113540453A (en) * 2020-08-27 2021-10-22 中南大学 Internal lithium-philic multi-confinement/induction hollow carbon composite framework of lithium metal cathode and preparation method thereof
CN115117303A (en) * 2021-03-18 2022-09-27 恒大新能源技术(深圳)有限公司 Lithium metal negative electrode, preparation method thereof and lithium secondary battery

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