CN113346074A - Electrode material with multilayer structure and preparation method thereof - Google Patents

Electrode material with multilayer structure and preparation method thereof Download PDF

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CN113346074A
CN113346074A CN202010137911.4A CN202010137911A CN113346074A CN 113346074 A CN113346074 A CN 113346074A CN 202010137911 A CN202010137911 A CN 202010137911A CN 113346074 A CN113346074 A CN 113346074A
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electrode material
multilayer structure
carbon
tin
monomer
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CN113346074B (en
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罗正汤
柳真晶
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Hong Kong University of Science and Technology HKUST
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Hong Kong University of Science and Technology HKUST
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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
    • H01M4/58—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 provides an electrode material with a multilayer structure, which comprises a carbon nano tube, a carbon layer attached to the surface of the carbon nano tube and a tin compound layer between the carbon nano tube and the carbon layer, wherein the tin compound layer is continuous and has the thickness of nanometer level. The invention also provides a preparation method of the electrode material with the multilayer structure, which comprises the following steps: polymerizing the monomer and the carbon nano tube in situ to obtain the carbon nano tube/polymer; dropwise adding a divalent tin ion solution, uniformly mixing, and removing the solvent to obtain a precursor; and annealing the precursor to obtain a product. The preparation method disclosed by the invention is simple in steps, low in raw material price and free of pollution, and is suitable for large-scale production, and the obtained electrode material with the multilayer structure effectively reduces the diffusion path of sodium ions, so that the rate capability is improved, and excellent conductivity and cycling stability are shown.

Description

Electrode material with multilayer structure and preparation method thereof
Technical Field
The invention relates to the field of batteries, in particular to an electrode material with a multilayer structure and a preparation method thereof.
Background
At present, the development of human society still depends heavily on traditional fossil energy such as coal, petroleum and natural gas. The unreasonable energy consumption structure can accelerate the exhaustion of fossil energy to cause energy crisis, and bring about a large amount of greenhouse gas emission and corresponding environmental problems, which is not beneficial to the sustainable development of human society. The renewable clean new energy industries such as solar energy, wind energy and the like are vigorously developed to become the trend of being unable to block. However, the new energy is unstable in power supply and is easily interfered by natural factors, so that a large-scale energy storage system needs to be introduced to supplement the smart grid so as to ensure stable input of electric energy and meet power supply requirements of different time periods and different areas. The sodium ion battery is regarded as a key device of a large-scale energy storage system by virtue of the characteristics of abundant sodium resource reserves, wide range of operable temperature and the like. The sodium ion battery has a working principle similar to that of the lithium ion battery, and realizes a charging and discharging process by shuttling sodium ions between a positive electrode and a negative electrode. However, compared with lithium ions, the difficulty of intercalation and deintercalation of sodium ions in electrode materials is increased by the larger mass and radius of the sodium ions, and when common lithium ion battery cathode materials are applied to sodium ion batteries, the electrochemical performance of the common lithium ion battery cathode materials is not ideal, so that the search for suitable electrode materials is the key for developing sodium ion battery technology.
Some tin compounds, such as tin dioxide, tin disulfide, etc., are desirable negative electrode materials for sodium ion batteries due to their higher theoretical capacity. However, the material is a semiconductor, the conductivity is poor, the high capacity is difficult to maintain under the condition of high current density, and large morphology change and volume change are easy to occur in the charging and discharging process, so that the material pulverization and dissolution are caused, and the cycle stability and the practical application of the material are influenced. At present, the introduction of carbon nanotubes is adopted to enhance the conductivity, stability and the like, but in such a way, the combination of tin compound particles obtained in a three-dimensional form with the carbon nanotubes is still weak in volume inhibition capacity of tin compounds, and the control of sodium ion diffusion is limited. Therefore, there is a high necessity for a new electrode material that overcomes the above-mentioned drawbacks.
Disclosure of Invention
In view of the above technical problems, an object of the present invention is to provide an electrode material with a multilayer structure, which effectively reduces the diffusion path of sodium ions, thereby improving the rate capability thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrode material of a multi-layered structure includes a carbon nanotube, a carbon layer attached to a surface of the carbon nanotube, and a tin compound layer between the carbon nanotube and the carbon layer, the tin compound layer being continuous and having a thickness of a nanometer order.
The tin compound layer of the present application is not in the prior art discontinuous particulate form, is continuous, and has a very small thickness, on the nanometer scale, in one embodiment about 5 nm. Compared with the three-dimensional micron-sized tin compound particles, the continuous tin compound layer with the thickness of nanometer level effectively reduces the diffusion path of ions such as sodium ions in the battery, thereby improving the rate capability of the battery. In addition, the carbon layer formed on the surface of the tin compound realizes a sandwich-like multilayer structure of the carbon nanotube/tin compound/carbon layer, which is more advantageous in suppressing the morphology and volume change of the tin compound, thereby being more advantageous in the cycle stability as an electrode material and being capable of effectively preventing the active material from falling off the carbon nanotube. Preferably, the carbon layer is an amorphous carbon layer.
Further, the compound layer of tin is tin disulfide (SnS)2) Tin (Sn) trisulfide2S3) Or tin sulfide (SnS). Preferably, the compound layer of tin is tin disulfide. Tin disulfide has a relatively high theoretical capacity (1000 mA h-1). In addition, tin disulfide has a unique layered structure with larger interlayer spacing, and stacking between layers through weaker van der waals forces is more beneficial to the diffusion process of ions such as sodium ions in the cell.
The second purpose of the invention is to provide a preparation method of the electrode material with a multilayer structure, which has simple steps, low price of raw materials, no pollution and suitability for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an electrode material with a multilayer structure comprises the following steps:
polymerizing the monomer and the carbon nano tube in situ to obtain the carbon nano tube/polymer;
dropwise adding a divalent tin ion solution, uniformly mixing, and removing the solvent to obtain a precursor;
and annealing the precursor to obtain a product.
After in situ polymerization, the tin ions are uniformly adsorbed on the surface of the carbon substrate, thereby spatially limiting the growth of tin compounds.
Further, the monomer and the carbon nano tube are polymerized in situ by uniformly mixing the monomer, the solution of the carbon nano tube and the photoinitiator and performing in the presence of ultraviolet light.
The solution of the carbon nanotubes refers to a solution obtained by uniformly dispersing the carbon nanotubes into a solvent, and any solvent commonly used in the art for dispersing carbon nanotubes may be suitable for the present application, for example, ethanol, isopropanol, or a mixture of water and isopropanol. Preferably, the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.
Further, the monomer is a nitrogen-containing monomer. The nitrogen-containing monomer can introduce nitrogen into the product, whereby the conductivity of the carbon nanotube can be improved, and furthermore, the binding energy between the tin compound and the carbon nanotube can be enhanced.
Further, the nitrogen-containing monomer is one or more of methacrylic acid gelatin, acrylamide or methylene bisacrylamide.
Further, the mass ratio of the carbon nano tube to the monomer is 1-10; the mass ratio of the carbon nano tube to the divalent tin ion is 0.2-12.
Further, the solvent was removed by lyophilization. The freeze-drying is carried out under the conditions of low pressure and low temperature, so that the solvent in the sample is directly sublimated, and the three-dimensional porous structure of the sample is maintained, and the sample has a larger specific surface area.
Further, the precursor is mixed with sulfur powder prior to annealing. Preferably, the mass ratio of the precursor to the sulfur powder is 0.5-5.
Further, the annealing process comprises the following steps: heating the tube furnace to 300-800 ℃ at a heating rate of 5-50 ℃/min under an inert gas atmosphere, keeping the temperature for 5-200 min, and naturally cooling
The term "carbon nanotube" herein includes single-walled carbon nanotubes and multi-walled carbon nanotubes.
The invention has the advantages of
The preparation method has simple steps, low price of raw materials and no pollution, and is suitable for large-scale production;
the electrode material with the multilayer structure effectively reduces the diffusion path of sodium ions, thereby improving the multiplying power performance;
the electrode material of the multilayer structure obtained by the invention has excellent conductivity and cycling stability.
Drawings
FIGS. 1a) and b) are transmission electron microscopy images of the product of example 1 according to the invention;
FIG. 2 is an X-ray diffraction pattern of the product of example 1 according to the present invention;
FIGS. 3a), b), c), d) are X-ray photoelectron spectra of the product of example 1 according to the present invention;
FIG. 4 shows the product of example 1 according to the invention at a current density of 200mA g1Cyclic performance of the time;
FIG. 5 shows the product of example 1 according to the invention at a current density of 50mA g1Cyclic performance of the time;
figure 6 shows the rate capability of the product of example 1 according to the invention (1C-500 mA g)1)；
FIG. 7 is an X-ray diffraction pattern of the product of example 2 according to the present invention;
FIG. 8 is a transmission electron micrograph of a product according to example 3 of the present invention;
FIG. 9 is an X-ray diffraction pattern of the product of example 3 according to the present invention;
FIG. 10 is a transmission electron micrograph of a product according to example 4 of the present invention;
FIG. 11 is an X-ray diffraction pattern of the product of example 4 according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Deionized water and isopropanol are mixed into a mixture according to the volume ratio of 1:1, then 20mg of multi-wall carbon nano-tubes are added, and the mixture is subjected to ultrasonic treatment for 1 hour to form a uniform and stable solution. To this solution, 10mg of methacrylic acid gelatin and 10. mu.L of 2-hydroxy-2-methyl-1-phenylpropanone as a photoinitiator were sequentially added and shaken for 20min to obtain a carbon nanotube/methacrylic acid solution. Exposing the carbon nanotube/methacrylic acid solution to 365nm ultraviolet lamp (light intensity of 1.35W/cm)2) Irradiating for 15min to polymerize the methacrylic acid monomer on the surface of the carbon nano tube. 1.34mL of a 0.15M stannous chloride solution was then added dropwise and stirred for 4h to ensure adsorption of the stannous ion by the polymer. After stirring, the resulting solution was frozen in a refrigerator for 1h, then placed in a freeze dryer and taken out after 2 days. And stirring and mixing the freeze-dried precursor and sulfur powder, and putting the mixture into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 0.67. And then, placing the quartz boat in a heating center of a tube furnace, introducing argon of 200sccm for 20min to take out residual air in the tube, heating the tube furnace to 550 ℃ at a heating rate of 35 ℃/min, annealing for 20min, opening a furnace cover, naturally cooling to obtain a product, and introducing argon of 50sccm in the heating and annealing processes.
The product obtained is observed by transmission electron microscopy, FIGS. 1a) and b) being transmission electron microscopy images at a scale of 100nm and 5nm, respectively. As shown in fig. 1a), the carbon nanotubes are uniformly dispersed, and the surface thereof is covered with a layered modifier. The sandwich-like multilayer structure of the product can be clearly seen enlarged as shown in fig. 1 b). The carbon nanotubes are arranged at the upper left part of the graph 1b), the surface of the carbon nanotubes (shown as the right side of the carbon nanotubes in the graph) is covered with a tin disulfide layer with the thickness of about 5nm, the interlayer distance of the tin disulfide layer is 0.59nm, and the whole tin disulfide layer has a nanoscale sheet structure. The tin disulfide is covered with an amorphous carbon layer about 2nm thick (shown on the right side of the tin disulfide). The crystal structure of the product can be further confirmed by X-ray diffraction pattern, and the result is shown in fig. 2. The upper curve in figure 2 is the product of example 1 and the lower curve is tin disulfide, and comparing the diffraction peak positions with the standard alignment chart shows that the characteristic peaks of the product are derived from tin disulfide. Fig. 3a) is an X-ray photoelectron spectrum of the product, confirming the presence of tin, sulfur, carbon, nitrogen and oxygen elements in the product. Fig. 3b), 3c) and 3d) are the results of high resolution scanning of nitrogen, tin and sulfur, respectively, and the peak positions thereof confirmed that tin is +4 valent and sulfur is-2 valent in the product, and the results confirmed nitrogen doping and sulfur doping of carbon nanotubes.
Preparation of electrode slice
The product, carbon black and polyvinylidene fluoride were mixed at a mass ratio of 70:20:10 and coated on a copper foil, which was then placed in a vacuum drying oven to dry for 24 hours at a temperature of 80 ℃. In a glove box with the water and oxygen concentration lower than 0.5ppm under the protection of nitrogen, assembling the dried electrode plate and a counter electrode sodium metal sheet into a CR2032 button cell for testing
The electrode sheet manufactured as above was subjected to a half cell test.
Fig. 4 and 5 show the cycle performance of the product. As shown in FIG. 4, the current density is 0.02-2.5V in the charging and discharging interval-200mA g1After 80 cycles, the capacity of the negative electrode of the sodium ion battery made of the product of example 1 was maintained at 417mAh g-1As shown in FIG. 5, the current density is set to be 0.02-2.5V in the charging and discharging interval-50mA g1After 60 cycles, the capacity of the negative electrode of the sodium ion battery made of the product of example 1 was maintained at 500mAh g-1And the left and the right show better cycling stability. As shown in FIG. 6, when the current densities were 50, 100, 200, 500, 1000, 1500, 2000 and 2500mA g, respectively-1The corresponding capacities of the electrodes are 738, 613, 538, 463, 411, 382, 360 and344mAh g-1. When the current density is again set to 50mA g-1The capacity is 700mAh g-1And the rate capability is higher.
Example 2
The procedure of example 1 above was repeated except that the freeze-dried sample was annealed directly at about 500 ° without adding sulfur powder to obtain tin dioxide dispersed on the carbon nanotubes. The annealing process may be carried out without introducing an inert gas, or with introducing air or oxygen. Figure 7 shows an X-ray diffraction pattern with the top curve being the product of this example and the bottom curve being tin dioxide, and the alignment of the characteristic peaks indicates that the product is characterized by peaks from tin dioxide.
Example 3
The operation procedure of the above example 1 was repeated except that the annealing temperature was 600 c and the annealing time was 60min, to finally obtain a product of a multi-layered structure of carbon nanotube/SnS/carbon layer. Fig. 8 shows a transmission electron micrograph of the product, and it can be seen that the surface of the carbon nanotube is uniformly covered with the layered modifier. FIG. 9 shows an X-ray diffraction pattern with the upper curve being the product of this example and the lower curve being the dititanium trisulfide, the alignment of the characteristic peaks indicating that the characteristic peaks of the products are all derived from dititanium trisulfide.
Example 4
The procedure of example 1 was repeated except that the annealing temperature was 600 ℃ and the annealing time was 90min to obtain carbon nanotubes/Sn2S3A product of a multi-layer structure of a/carbon layer. Fig. 10 shows a transmission electron micrograph of the product, and it can be seen that the surface of the carbon nanotube is uniformly covered with the layered modifier. Figure 11 shows an X-ray diffraction pattern with the upper curve being the product of this example and the lower curve being stannous sulfide, and the alignment of the characteristic peaks indicates that the characteristic peaks of the product are all from stannous sulfide.
Example 5
Deionized water and isopropanol are mixed into a mixture according to the volume ratio of 5:1, then 20mg of multi-wall carbon nano-tubes are added, and the mixture is subjected to ultrasonic treatment for 2 hours to form a uniform and stable solution. To this solution, 20mg of acrylamide and 50L of 2-hydroxy-2-methyl-1-benzene as a photoinitiator were added in this orderAcetone and oscillating for 60min to obtain the carbon nano tube/acrylamide solution. The carbon nanotube/acrylamide solution was exposed to a 365nm UV lamp (light intensity of 1.35W/cm)2) Irradiating for 60min to polymerize acrylamide monomer on the surface of the carbon nanotube. 5mL of a stannous chloride solution with a concentration of 0.15M were then added dropwise and stirred for 12h to ensure adsorption of the stannous ions by the polymer. After stirring, the resulting solution was frozen in a refrigerator for 3 hours, then placed in a freeze dryer and taken out after 3 days. And stirring and mixing the freeze-dried precursor and sulfur powder, and putting the mixture into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 5. And then, placing the quartz boat in a heating center of a tube furnace, introducing 200sccm of argon for 30min to take out residual air in the tube, heating the tube furnace to 800 ℃ at a heating rate of 50 ℃/min, annealing for 200min, then rapidly cooling, and introducing 500sccm of argon in the heating and annealing processes. And cooling the furnace to obtain the product.
Example 6
Deionized water and isopropanol are mixed into a mixture according to the volume ratio of 3:1, then 20mg of multi-wall carbon nano-tubes are added, and the mixture is subjected to ultrasonic treatment for 3 hours to form a uniform and stable solution. To this solution, 2mg of methylene bisacrylamide and 5L of 2-hydroxy-2-methyl-1-phenylpropanone as a photoinitiator were added in this order, and oscillation was carried out for 10min to obtain carbon nanotubes/methylene bisacrylamide. Exposing the carbon nanotube/methylene bisacrylamide solution to a 365nm ultraviolet lamp (light intensity of 1.35W/cm)2) Irradiating for 10min to polymerize methylene bisacrylamide monomer on the surface of the carbon nanotube. Then 0.1mL of stannous chloride solution with concentration of 0.15M is added dropwise and stirred for 1h to ensure adsorption of the polymer to stannous ions. After stirring, the resulting solution was frozen in a refrigerator for 1h, then placed in a freeze dryer and taken out after 1 day. And stirring and mixing the freeze-dried precursor and sulfur powder, and putting the mixture into a quartz boat, wherein the mass ratio of the precursor to the sulfur powder is 0.5. And then, placing the quartz boat in a heating center of a tube furnace, introducing 200sccm argon for 5min to take out residual air in the tube, heating the tube furnace to 300 ℃ at a heating rate of 5 ℃/min, annealing for 5min, then rapidly cooling, and introducing 1sccm argon in the heating and annealing processes. To be treatedAnd cooling the furnace to obtain the product.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. It is not intended to be exhaustive or to limit all embodiments to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. All obvious changes and modifications which are within the technical scope of the invention are covered by the invention.

Claims (10)

1. An electrode material having a multilayer structure, comprising a carbon nanotube, a carbon layer attached to a surface of the carbon nanotube, and a tin compound layer between the carbon nanotube and the carbon layer, the tin compound layer being continuous and having a thickness of the order of nanometers.
2. The electrode material of claim 1, wherein the tin compound layer is tin disulfide, tin trisulfide, or tin sulfide.
3. The method for preparing an electrode material of a multilayer structure according to claim 1, comprising the steps of:
in-situ polymerizing the monomer and the carbon nano tube to obtain the carbon nano tube/polymer;
dropwise adding a divalent tin ion solution, uniformly mixing, and removing the solvent to obtain a precursor;
and annealing the precursor to obtain a product.
4. The method for preparing an electrode material with a multilayer structure according to claim 3, wherein the in-situ polymerization of the monomer and the carbon nanotubes is performed under the action of ultraviolet light by uniformly mixing the monomer, a solution of the carbon nanotubes and a photoinitiator.
5. The method for producing an electrode material of a multilayer structure according to claim 3 or 4, wherein the monomer is a nitrogen-containing monomer.
6. The method for preparing an electrode material with a multilayer structure according to claim 5, wherein the nitrogen-containing monomer is one or more of methacrylic acid gelatin, acrylamide or methylene bisacrylamide.
7. The method for preparing the electrode material of the multilayer structure according to claim 3 or 4, wherein the mass ratio of the carbon nanotubes to the monomer is 1 to 10; the mass ratio of the carbon nano tube to the divalent tin ion is 0.2-12.
8. The method for producing an electrode material of a multilayer structure according to claim 3 or 4, wherein the removal of the solvent is performed by freeze-drying.
9. The method for producing an electrode material of a multilayer structure according to claim 3 or 4, wherein a precursor is mixed with sulfur powder before the annealing.
10. The method for preparing an electrode material of a multilayer structure according to claim 3 or 4, wherein the annealing process comprises: heating the tube furnace to 300-800 ℃ at a heating rate of 5-50 ℃/min, keeping the temperature for 5-200 min, and then naturally cooling.
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