CN116632224B - Negative electrode material, preparation method and application thereof - Google Patents

Negative electrode material, preparation method and application thereof Download PDF

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CN116632224B
CN116632224B CN202310906713.3A CN202310906713A CN116632224B CN 116632224 B CN116632224 B CN 116632224B CN 202310906713 A CN202310906713 A CN 202310906713A CN 116632224 B CN116632224 B CN 116632224B
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alloy
ges
anode material
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composite carbon
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CN116632224A (en
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徐宝和
程磊
邓鹏�
丁瑶
冯建慧
吴斌
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Pawa Changsha New Energy Technology Co ltd
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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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The invention belongs to the technical field of battery materials. The invention firstly discloses GeS 2 The @ alloy @ C anode material comprises an inner layer and an outer layer, wherein the inner layer is an alloy material of composite carbon, and the outer layer is GeS 2 . Secondly, the preparation method of the anode material is disclosed, an alloy organic frame material is obtained firstly, then the alloy organic frame material is subjected to high-temperature pyrolysis to obtain an alloy material of composite carbon, and then GeS is composited on the surface of the alloy material of the composite carbon 2 A layer. The battery assembled by the negative electrode material provided by the invention has more excellent cycle performance and rate performance.

Description

Negative electrode material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a negative electrode of a secondary battery and a preparation method thereof.
Background
Alkali ion batteries are considered to be the most desirable energy storage elements because of their high energy density, long cycle life, and no memory effect. The negative electrode is one of the key components of an alkaline ion battery. The negative electrode material of the secondary battery mainly includes carbon-based negative electrode, alloy-based negative electrode, transition metal oxide/chalcogenide, and the like. The carbon negative electrode has better conductivity but lower capacity; the alloy type negative electrode material has higher storage capacity, higher voltage platform, larger volume change and poorer cycle performance; the transition metal compound has advantages of various kinds, excellent electrochemical capacity, etc., but has serious voltage hysteresis. Research workers have also been devoted to research into negative electrode materials excellent in cycle performance and rate performance.
Disclosure of Invention
The invention aims to provide a negative electrode material GeS with excellent long-cycle performance and rate performance 2 An @ alloy @ C anode material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following specific technical solutions.
GeS (GeS) 2 The @ alloy @ C anode material comprises an inner layer and an outer layer, wherein the inner layer is an alloy material of composite carbon, and the outer layer is GeS 2 。
In a further preferred embodiment, the GeS 2 The molar ratio of the alloy material of the composite carbon is 3-10: 100.
in a further preferred embodiment, the alloy material consists of at least two of Sb, sn, bi, zn.
In a further preferred embodiment, the carbon in the alloy material of the composite carbon is 5-8% by mass.
Based on the same inventive concept, the invention provides the GeS 2 The preparation method of the @ alloy @ C anode material comprises the following steps:
dissolving soluble salts and organic complexing agents of at least two metals in Sb, sn, bi, zn in deionized water or an organic solvent to perform hydrothermal reaction or solvothermal reaction; washing the product after the reaction to obtain an alloy organic frame material;
high-temperature cracking alloy organic frame material to obtain alloy material of composite carbon;
introducing nitrogen or inert gas into the calciner to exhaust air, then placing the alloy material of the composite carbon at the lower tuyere of the calciner, and placing GeS 2 Placing at the upper tuyere of the calciner, and calcining to obtain GeS 2 Negative electrode of @ alloy @ CA material.
In a further preferred embodiment, the soluble salt is at least one of sulfate, nitrate, acetate, chloride.
In a further preferred embodiment, the organic complexing agent is at least one of fumaric acid, 2-methylimidazole, trimesic acid, isophthalic acid, and glutamic acid.
In a further preferred embodiment, the organic solvent is at least one of ethanol, methanol, ethylene glycol, acetone, N-dimethylformamide.
In a further preferred embodiment, the molar ratio of the soluble salts of the at least two metals to the organic complexing agent is 1: 5-10.
In a further preferred scheme, the total concentration of the soluble salts of the at least two metals and the organic complexing agent in deionized water or an organic solvent is 0.1-2 mol/L.
In a further preferred scheme, the temperature of the hydrothermal reaction or the solvothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction or the solvothermal reaction is 10-20 hours.
In a further preferred embodiment, the pyrolysis atmosphere is an argon or nitrogen atmosphere; the high-temperature cracking temperature is 500-700 ℃ and the high-temperature cracking time is 2-5 h.
In a further preferred scheme, the calcination temperature is 700-800 ℃ and the calcination time is 1-2 h.
In addition, the invention provides a battery comprising the anode material.
The invention has the following obvious beneficial effects:
the invention sublimates and compounds GeS on the surface of the alloy material of the compound carbon 2 The cycle performance and the multiplying power performance of the battery assembled by the obtained anode material are more excellent.
According to the invention, geS is ingeniously placed at the upper and lower airflow positions of the calciner respectively 2 And the alloy material of the composite carbon can fully utilize the prior equipment to realize the aim of the invention, and greatly relieve the pressure of the new process on the equipment.
The preparation method provided by the invention has the advantages of simple process, reliability, high repeatability and low energy consumption.
The invention uses carbon, alloy and GeS 2 The method is skillfully combined together, and a new idea is developed for innovation and development of the negative electrode material of the alkali metal battery.
Drawings
FIG. 1 is a GeS prepared in example 1 2 SEM image of @ sbbi @ c negative electrode material.
Detailed Description
The invention provides a negative electrode material GeS with excellent long-cycle performance and multiplying power performance 2 An @ alloy @ C, and a preparation method and application thereof.
First, the present invention provides a GeS 2 The @ alloy @ C anode material comprises an inner layer and an outer layer, wherein the inner layer is an alloy material of composite carbon, and the outer layer is GeS 2 。
GeS 2 Is a monocrystal-like material, has tough and wide ion channels and good ion conductivity, but radial stress is easy to generate if the ion transmission channels are too long; the metal alloy-carbon composite material has good electron conductivity, but ion transmission is relatively slow; metal alloy @ C material and GeS 2 At the junction, a schottky heterojunction can be formed, thereby accelerating ion and electron transport at the interface. Therefore, by combining the advantages of the materials, the composite material can realize good ion/electron transmission dynamics and structural stability, thereby showing good electrochemical performance.
In selecting a particular alloy composition, a metal that is itself capable of storing energy should be selected. In a specific embodiment of the present invention, the alloy material consists of at least two of Sb, sn, bi, zn.
In the above-mentioned anode material, the content of carbon in the alloy material of the composite carbon and the outer layer GeS may be further optimized 2 Is contained in the composition. GeS (GeS) 2 The material can undergo conversion reaction and alloying reaction in the potassium storage process, and has higher energy storage capacity than the pure alloy material; however, if GeS 2 The layers are too thick, the electron conductivity of the material will weaken, and radial stresses are easily generated; the carbon material has good electron conductivityBut the ionic conductivity is poor and the capacity is low. Therefore, geS 2 And the change of the carbon content has great influence on the reaction dynamics, the structural stability and the energy storage capacity of the material.
In the specific embodiment of the present invention, preferably the GeS 2 The molar ratio of the alloy material of the composite carbon is 3-10: 100; the mass percentage of carbon in the alloy material of the composite carbon is 5-8%.
Next, the present invention provides the above GeS 2 The preparation method of the @ alloy @ C anode material comprises the following steps:
dissolving soluble salts and organic complexing agents of at least two metals in Sb, sn, bi, zn in deionized water or an organic solvent to perform hydrothermal reaction or solvothermal reaction; washing the product after the reaction to obtain an alloy organic frame material;
high-temperature cracking alloy organic frame material to obtain alloy material of composite carbon;
introducing nitrogen or inert gas into the calciner to exhaust air, then placing the alloy material of the composite carbon at the lower tuyere of the calciner, and placing GeS 2 Placing at the upper tuyere of the calciner, and calcining to obtain GeS 2 An @ alloy @ C anode material.
Alloy material of composite carbon is synthesized by combining metal organic framework as precursor and high-temperature pyrolysis, and finally GeS is adopted 2 Sublimation composite sintering to obtain GeS 2 Composite @ alloy @ C. Will GeS 2 Placing at the upper tuyere, placing alloy material of composite carbon at the lower tuyere, geS 2 High-temperature sublimation occurs at the upper tuyere, and gas generated by sublimation is transferred to the alloy material of the composite carbon at the lower tuyere through air flow, so that GeS is realized 2 And the alloy material of the composite carbon is effectively compounded. And the thickness of the composite layer is controllable, the element distribution is uniform, and the structural reversibility and the electrochemical capacity of the anode material can be effectively improved.
1. In the process of synthesizing the metal organic framework material through the hydrothermal reaction or the solvothermal reaction:
the type of the soluble salt of the metal is not particularly limited as long as it is soluble in water or an organic solvent. In a specific embodiment of the present invention, the soluble salt is at least one of sulfate, nitrate, acetate, chloride.
The organic complexing agent is used for forming complex precipitate or floccule, namely the metal organic framework material. Organic complexing agents having the above-mentioned effects can be used as the reaction raw materials of the present invention. In a specific embodiment of the present invention, the organic complexing agent is at least one of fumaric acid, 2-methylimidazole, trimesic acid, isophthalic acid, and glutamic acid.
The soluble salt of the metal and the organic complexing agent can be subjected to hydrothermal reaction in deionized water or solvothermal reaction in an organic solvent. In a specific embodiment of the present invention, the organic solvent is at least one of ethanol, methanol, ethylene glycol, acetone, and N, N-dimethylformamide. The solvent is specifically selected based on the fact that complete dissolution of the selected organic complexing agent can be achieved. For example, 2-methylimidazole is weakly selected as the organic complexing agent, and water, methanol or ethanol is selected as the solvent, but if isophthalic acid is selected as the organic complexing agent, the solvent is selected from organic solvents such as methanol, ethanol, acetone, etc.
Based on the technical idea of the present invention, a person skilled in the art can adjust carbon, alloy materials and GeS in the anode material according to actual needs 2 The amount in the anode material and the relevant parameters of the amount of each reaction raw material in the reaction process are known in the specific hydrothermal reaction or solvothermal reaction process. In a specific embodiment of the present invention, the molar ratio of the soluble salts of the at least two metals to the organic complexing agent is 1: 5-10; the total concentration of the soluble salts of at least two metals and the organic complexing agent in deionized water or an organic solvent is 0.1-2 mol/L.
Likewise, the temperature of the hydrothermal reaction or solvothermal reaction can be obtained by a plurality of experiments by a person skilled in the art in light of the technical idea of the present invention. In a specific embodiment of the invention, the temperature of the hydrothermal reaction or the solvothermal reaction is 120-180 ℃. The hydrothermal reaction or solvothermal reaction temperature is lower than 120 ℃, and the organic complexing agent may be incompletely complexed, so that the final product yield is affected; the hydrothermal or solvothermal reaction temperature is greater than 180 ℃, and the organic complexing agent may decompose or convert, thereby rendering the final complex precipitate phase impure and ultimately affecting the structural uniformity of the material. The time of the hydrothermal reaction or solvothermal reaction can be adaptively adjusted according to the actual reaction progress. In the specific embodiment of the invention, the time of the hydrothermal reaction or the solvothermal reaction is 10-20 h.
2. During pyrolysis of the metal organic framework:
in a specific embodiment of the invention, the pyrolysis atmosphere is an argon or nitrogen atmosphere; the high-temperature cracking temperature is 500-700 ℃ and the high-temperature cracking time is 2-5 h. The high-temperature cracking temperature is lower than 500 ℃, and the organic framework structure cannot be completely converted into a carbon-based material; the pyrolysis temperature is higher than 700 ℃, and the carbon-based material may harden or react with oxygen atoms in the frame to volatilize resulting in carbon loss. However, those skilled in the art can still make further studies on the pyrolysis temperature as long as the pyrolysis temperature can achieve the object of the present invention.
3. In the composite GeS 2 In the process (1), the temperature of the calciner is higher than GeS 2 Is used for the sublimation temperature of the glass fiber reinforced plastic material. GeS (GeS) 2 And heating and sublimating the alloy material at the upper air opening of the calciner, and enabling the alloy material to flow to the composite carbon at the lower air opening along with airflow. GeS (GeS) 2 When contacting with the alloy material of the composite carbon, the sublimated steam forms a special bond with the alloy material of the composite carbon, and is effectively compounded on the surface of the alloy material of the composite carbon. In the specific embodiment of the invention, the calcination temperature is 700-800 ℃ and the calcination time is 1-2 h.
In addition, the invention provides a battery comprising the anode material.
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
(1) Dissolving 0.01mol of antimony nitrate, 0.01mol of bismuth nitrate and 0.16mol of isophthalic acid in 100ml of methanol solvent, performing solvothermal reaction at 160 ℃ for 18 hours, and washing with water and alcohol after the reaction is finished to obtain the SbBi-containing metal organic frame material; then carrying out high-temperature pyrolysis for 5 hours at 600 ℃ in nitrogen atmosphere to obtain an alloy material of SbBi@C;
(2) 1mmol GeS 2 Placing the alloy material of SbBi@C prepared in the step (1) at a position close to an air inlet in a nitrogen atmosphere, and calcining at 750 ℃ for 1h to obtain GeS 2 The @ SbBi @ C anode material is shown in FIG. 1. The graph shows that the material in the graph has uniform morphology distribution, no obvious tiny particles are arranged around the graph, and the material surface has no unevenly distributed granular compound, so that the structural integrity of the composite material is strong, and the surface coating layer is perfectly coated on the surface of the substrate material and is perfectly attached to the substrate material.
Comparative example 1
Comparative example 1 differs from example 1 only in that there is no composite GeS 2 Is carried out by a method comprising the steps of.
Dissolving 0.01mol of antimony nitrate, 0.01mol of bismuth nitrate and 0.16mol of isophthalic acid in 100ml of methanol solvent, performing solvothermal reaction at 160 ℃ for 18 hours, and washing with water and alcohol after the reaction is finished to obtain the SbBi-containing metal organic frame material; then the alloy material of SbBi@C is obtained by high-temperature pyrolysis for 5 hours at 600 ℃ under the nitrogen atmosphere.
Comparative example 2
Comparative example 2 differs from example 1 in that: geS (GeS) 2 The compounding mode of (2) is solid phase mixing.
(1) Dissolving 0.01mol of antimony nitrate, 0.01mol of bismuth nitrate and 0.16mol of isophthalic acid in 100ml of methanol solvent, performing solvothermal reaction at 160 ℃ for 18 hours, and washing with water and alcohol after the reaction is finished to obtain the SbBi-containing metal organic frame material; then carrying out high-temperature pyrolysis for 5 hours at 600 ℃ in nitrogen atmosphere to obtain an alloy material of SbBi@C;
(2) 1mmol GeS 2 Mixing the alloy material with the SbBi@C prepared in the step (1) in a solid phase to obtain GeS 2 The @ SbBi @ C anode material.
Example 2
(1) Dissolving 0.01mol of tin nitrate, 0.01mol of bismuth nitrate and 0.10mol of glutamic acid in 1000ml of water, performing hydrothermal reaction at 180 ℃ for 10 hours, and washing with water and alcohol after the reaction is finished to obtain the SnBi-containing metal organic frame material; then carrying out high-temperature pyrolysis for 5 hours at 500 ℃ in nitrogen atmosphere to obtain an alloy material of SnBi@C;
(2) Will 0.5mmol GeS 2 Placing the alloy material of SnBi@C prepared in the step (1) at an air inlet under nitrogen atmosphere, and calcining at 700 ℃ for 1h to obtain GeS 2 @SnBi@C negative electrode material.
Example 3
(1) Dissolving 0.01mol of zinc sulfate, 0.01mol of bismuth acetate and 0.2mol of 2-methylimidazole in 200ml of acetone solvent, performing solvothermal reaction at 120 ℃ for 20h, and washing with water and alcohol after the reaction is finished to obtain a ZnBi-containing metal organic frame material; then carrying out high-temperature pyrolysis for 3 hours at 700 ℃ in nitrogen atmosphere to obtain an alloy material of ZnBi@C;
(2) Will 0.3mmol GeS 2 Placing the alloy material of ZnBi@C prepared in the step (1) at an air inlet under the nitrogen atmosphere, placing the alloy material at the air outlet, and calcining at 750 ℃ for 1h to obtain GeS 2 @ ZnBi @ C anode material.
Example 4
(1) Dissolving 0.01mol of tin nitrate, 0.01mol of zinc chloride and 0.16mol of fumaric acid in 100ml of ethanol solvent, performing solvothermal reaction at 160 ℃ for 15 hours, and washing with water and alcohol after the reaction is finished to obtain the SnZn-containing metal organic frame material; then carrying out high-temperature pyrolysis for 4 hours at 600 ℃ in nitrogen atmosphere to obtain an alloy material of SnZn@C;
(2) 1mmol GeS 2 An air inlet arranged in nitrogen atmosphere is arranged1) Placing the prepared SnZn@C alloy material in an air outlet, calcining at 800 ℃ for 1h to obtain GeS 2 Snzn@c negative electrode material.
Example 5
(1) Dissolving 0.01mol of stannic chloride, 0.01mol of zinc sulfate, 0.01mol of bismuth nitrate and 0.24mol of trimesic acid in 200ml of N, N-dimethylformamide solvent, performing solvothermal reaction at 160 ℃ for 15 hours, and washing with water and alcohol after the reaction is finished to obtain the SnZn-containing metal organic frame material; then carrying out high-temperature pyrolysis for 4 hours at 600 ℃ in nitrogen atmosphere to obtain an alloy material of SnZnBi@C;
(2) 1mmol GeS 2 Placing the alloy material of SnZnBi@C prepared in the step (1) at an air inlet under the atmosphere of nitrogen, and calcining at 800 ℃ for 1h to obtain GeS 2 @SnZnBi@C negative electrode material.
The battery assembly was completed by the following method:
the materials obtained in examples 1-5 and comparative examples 1-2 are taken as cathode materials, and are mixed with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, N-methylpyrrolidone (NMP) is taken as solvent, and the mixture is stirred and mixed for 2 hours in a small beaker according to the rotating speed of 800r/min, so as to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass to a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 14mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. The separator used in the battery is glass fiber, the alkali metal sheet is a manually punched metal sodium block (diameter is 14 mm), and the electrolyte is 1.0M NaCF 3 SO 3 A solution dissolved in dimethyl ether (DME).
After the battery is assembled and aged for 12 hours, a charge and discharge test is carried out, and the sample is activated for 3 circles at 0.1C under the voltage of 0.1-3.0V and then circulated for 200 circles at the multiplying power of 2C. The results are shown in Table 1.
TABLE 1
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. GeS (GeS) 2 The @ alloy @ C anode material is characterized by comprising an inner layer and an outer layer, wherein the inner layer is an alloy material of composite carbon, and the outer layer is GeS 2 The method comprises the steps of carrying out a first treatment on the surface of the The alloy material is composed of at least two of Sb, sn, bi, zn.
2. GeS according to claim 1 2 An @ alloy @ C anode material characterized in that the GeS 2 The molar ratio of the alloy material of the composite carbon is 3-10: 100; the mass percentage of carbon in the alloy material of the composite carbon is 5-8%.
3. GeS according to claim 1 or 2 2 The preparation method of the @ alloy @ C anode material is characterized by comprising the following steps of:
dissolving soluble salts and organic complexing agents of at least two metals in Sb, sn, bi, zn in deionized water or an organic solvent to perform hydrothermal reaction or solvothermal reaction; washing the product after the reaction to obtain an alloy organic frame material;
high-temperature cracking alloy organic frame material to obtain alloy material of composite carbon;
introducing nitrogen or inert gas into the calciner to exhaust air, then placing the alloy material of the composite carbon at the lower tuyere of the calciner, and placing GeS 2 Placing at the upper tuyere of the calciner, and calcining to obtain GeS 2 An @ alloy @ C anode material.
4. A GeS according to claim 3 2 The preparation method of the @ alloy @ C anode material is characterized by comprising the following steps ofThe soluble salt is at least one of sulfate, nitrate, acetate and chloride; the organic complexing agent is at least one of fumaric acid, 2-methylimidazole, trimesic acid, isophthalic acid and glutamic acid; the organic solvent is at least one of ethanol, methanol, glycol, acetone and N, N-dimethylformamide.
5. GeS according to claim 3 or 4 2 The preparation method of the @ alloy @ C anode material is characterized in that the molar ratio of the soluble salts of at least two metals to the organic complexing agent is 1: 5-10; the total concentration of the soluble salts of at least two metals and the organic complexing agent in deionized water or an organic solvent is 0.1-2 mol/L.
6. A GeS according to claim 3 2 The preparation method of the @ alloy @ C anode material is characterized in that the temperature of the hydrothermal reaction or the solvothermal reaction is 120-180 ℃.
7. A GeS according to claim 3 2 The preparation method of the @ alloy @ C anode material is characterized by comprising the following steps of,
the high-temperature cracking atmosphere is argon or nitrogen atmosphere; the high-temperature cracking temperature is 500-700 ℃.
8. A GeS according to claim 3 2 The preparation method of the @ alloy @ C anode material is characterized in that the calcining temperature is 700-800 ℃.
9. A battery comprising the GeS of claim 1 or 2 2 GeS prepared by @ alloy @ C anode material or preparation method of any one of claims 3-8 2 An @ alloy @ C anode material.
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