CN111573633A - Preparation method and application of carbon-coated tin selenide negative electrode material - Google Patents
Preparation method and application of carbon-coated tin selenide negative electrode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007773 negative electrode material Substances 0.000 title claims description 15
- 238000000137 annealing Methods 0.000 claims abstract description 20
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- 238000000034 method Methods 0.000 claims abstract description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 15
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
A preparation method and application of a carbon-coated tin selenide cathode material belong to the technical field of sodium ion batteries. The SnSe semiconductor material synthesized by calcination is coated with a compact and uniform carbon layer by adopting a method of high-energy ball milling and annealing treatment, so that the electrochemical properties such as reversible specific capacity, cycle performance and the like are greatly improved. By a high-energy ball milling method, a uniform carbon source is introduced to the surface of the material while the particle size of the SnSe material particles is reduced, and a product can be obtained by annealing treatment. The preparation method disclosed by the invention is easy to operate, simple in process and low in cost, so that the preparation method has a wide application prospect. The prepared composite material has good electrochemical properties, including higher reversible specific capacity, good cycle performance and the like.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method and application of a carbon-coated tin selenide negative electrode material.
Background
In current advanced mobile devices such as mobile phones, notebook computers or pure electric vehicles, the lithium ion battery is an electrochemical secondary battery with the highest use frequency, and has the characteristics of high rated voltage, high energy density, good cycle performance, good safety, wide working temperature range, low pollution, unobvious self-discharge phenomenon, no memory effect and the like, so the current lithium ion battery becomes a preferred energy storage battery. However, considering that the lithium salt resource required by the current lithium ion battery cathode material has high cost and only supports three decades of human use at the current consumption level, the sustainability and cost-effectiveness of the lithium ion battery will limit its large-scale application, and therefore, people need to develop new high-performance secondary batteries as energy storage devices.
Sodium element is much more abundant in earth crust than lithium element, and can easily supply sufficient sodium source, so sodium ion batteries have recently attracted much attention. The principle and structure of the sodium ion battery are similar to those of the lithium ion battery, the sodium ion battery is a rocking chair type battery, energy storage is realized by embedding and separating sodium ions, and the sodium ion battery has approximate charging and discharging voltage intervals. However, the radius of sodium ions is larger than that of lithium ions, which causes larger volume strain of the electrode material during ion extraction, and has a certain influence on the structural stability of the material. The negative electrode material is one of key materials of the sodium ion battery, the current commercial sodium ion battery negative electrode material is mainly hard carbon, the hard carbon has a first intercalation capacity of 240mAh/g under a current density of 25mA/g, the intercalation capacity is kept at 200mAh/g after 100 cycles, and the good cycle performance is achieved. Therefore, the negative electrode material suitable for the development of the sodium ion battery has higher specific capacity while providing better cycling stability.
The tin selenide (SnSe) cathode material is a P-type semiconductor material with an orthorhombic crystal structure (the energy band gap is 0.9-1.3 eV). Among SnSe, Se having a valence of +2 is more electronegative than Sn having a valence of + 2. Some studies report the electrochemical reaction mechanism and performance of the SnSe as the lithium ion battery cathode material, however, the SnSe directly used as the sodium ion battery cathode material shows a high reversible capacity of more than 700mAh/g, but the cycling stability is poor, the residual specific capacity after 50 cycles is 220mAh/g, and the capacity retention rate is only 28.5%.
Disclosure of Invention
The invention aims to solve the problems of poor rate performance and poor cycle stability caused by poor conductivity of a SnSe cathode material and serious volume expansion of the material in an electrochemical cycle process, and provides a preparation method and application of a carbon-coated tin selenide cathode material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon-coated tin selenide negative electrode material comprises the following specific steps:
the method comprises the following steps: mixing Sn powder and Se powder according to the weight ratio of 1:1, transferring the mixture into a vacuum quartz tube after mixing, and performing high-temperature calcination by using a tube furnace;
step two: grinding and sieving the product SnSe powder obtained by calcining, and mixing the sieved product with a carbon source;
step three: carrying out high-energy ball milling treatment in an inert atmosphere, and screening to obtain a product;
step four: annealing treatment is carried out to form SnSe powder coated with a carbon layer on the surface.
The carbon-coated tin selenide cathode material is applied to a sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that: the invention uses a simple and easy-to-operate high-temperature solid-phase synthesis method, the temperature is controlled to be 590 ℃, and the precursor of the SnSe semiconductor material is synthesized. The compounding of the carbon layer adopts the mode of combining the high-energy ball milling and the annealing treatment, the distribution uniformity of the carbon layer is effectively improved, the thickness of the carbon layer is controllable, the carbon layer and the surface of the SnSe material are tightly combined, and the volume expansion of the SnSe material generated in the charging and discharging process is obviously inhibited. In addition, the carbon layer formed by annealing treatment contains an amorphous carbon material, and the larger interlayer spacing of the amorphous carbon material provides certain capacity for sodium ion intercalation, so that the reversible specific capacity of the material as a sodium ion battery negative electrode material is improved.
According to the invention, a high-energy ball milling and annealing treatment method is adopted for the SnSe semiconductor material synthesized by calcination, and a compact and uniform carbon layer is coated on the surface of the SnSe semiconductor material, so that the electrochemical properties such as reversible specific capacity, cycle performance and the like can be greatly improved. By a high-energy ball milling method, a uniform carbon source is introduced to the surface of the material while the particle size of the SnSe material particles is reduced, and a product can be obtained by annealing treatment. The preparation method disclosed by the invention is easy to operate, simple in process and low in cost, so that the preparation method has a wide application prospect. The prepared composite material has good electrochemical properties, including higher reversible specific capacity, good cycle performance and the like.
Drawings
Fig. 1 is an SEM image of a tin selenide composite coated with a carbon layer prepared in example 1;
fig. 2 is a raman spectrum of the tin selenide composite material coated with a carbon layer prepared in example 1;
FIG. 3 is a cyclic voltammogram of the first two cycles of the cell;
FIG. 4 is an electrochemical impedance spectrum of a battery;
FIG. 5 is a graph showing the charge and discharge curves of a battery;
FIG. 6 is a graph of the cycling performance of a battery;
FIG. 7 is a graph of rate performance of a battery;
FIG. 8 is a graph of the cycling performance of the cell of example 2;
fig. 9 is a graph of the cycle performance of the cell of example 3.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The invention adopts a high-temperature solid-phase synthesis method, and adopts raw materials of Se powder and Sn powder to synthesize the SnSe material by sintering. During sintering, SnSe semiconductor material having an orthorhombic crystal structure is formed. And mixing the carbon source and the SnSe material according to the mass ratio, and transferring the mixture into a ball milling tank in an argon atmosphere for high-energy ball milling to uniformly disperse the carbon source on the surface of the SnSe material. And transferring the mixture obtained by screening into a quartz tube filled with hydrogen and argon atmosphere, and carrying out annealing treatment to obtain a product. The method realizes the compact and uniform coating of the carbon layer on the surface of the SnSe material, reduces the volume effect of the material in the circulation process, simultaneously improves the conductivity and improves the electrochemical performance of the material.
According to the invention, the SnSe material is subjected to high-energy ball milling-calcined carbon layer coating modification, so that a tightly and uniformly combined carbon layer is reduced on the surface of the SnSe material while the granularity of the SnSe material is further reduced, and the electrochemical cycle stability is greatly improved while the high reversible capacity is maintained.
The first embodiment is as follows: the embodiment describes a preparation method of a carbon-coated tin selenide negative electrode material, which comprises the following specific steps:
the method comprises the following steps: mixing Sn powder and Se powder according to the weight ratio of 1:1, transferring the mixture into a vacuum quartz tube after mixing, and performing high-temperature calcination by using a tube furnace;
step two: grinding and sieving the product SnSe powder obtained by calcining, and mixing the sieved product with a carbon source;
step three: carrying out high-energy ball milling treatment in an inert atmosphere, and screening to obtain a product;
step four: annealing treatment is carried out to form SnSe powder coated with a compact and uniform carbon layer on the surface.
The second embodiment is as follows: in the first step, the high-temperature calcination is carried out at 590 ℃, the time is 72 hours, and the vacuum degree is less than or equal to 200 Pa.
The third concrete implementation mode: in the second step of the preparation method of the carbon-coated tin selenide anode material, the mass ratio of the carbon source to the total mixture is 10 wt.% to 40 wt.%.
The fourth concrete implementation mode: in the second step, the carbon source is one or a combination of glucose, sucrose or phenolic resin. The selected carbon source is easily obtained, can achieve the required effect and has low cost.
The fifth concrete implementation mode: in the third step, the rotation speed of the high-energy ball mill is 350rpm, and the time is 30 min. The high-energy ball milling at 350rpm plays a role in refining particles, and the low-rotation-speed effect is poor; the carbon source is uniformly dispersed within 30min, and the glucose and the sucrose are in a molten state by virtue of heat generated by high-energy ball milling, so that the glucose and the sucrose are favorably dispersed on the surface of the coated object SnSe.
The sixth specific implementation mode: in the fourth step, the annealing temperature is 700-800 ℃ and the time is 3-5 hours. The temperature of the annealing treatment is 700-800 ℃, the reduced carbon layer is ensured to have certain graphitization degree, and the carbon source is ensured to be fully reduced into the carbon layer within 3-5 hours, so that carbonization is complete.
The seventh embodiment: an application of the carbon-coated tin selenide negative electrode material prepared in any one of the first to sixth embodiments is to apply the carbon-coated tin selenide negative electrode material to a sodium ion battery.
Example 1:
se powder and Sn powder are mixed according to a molar ratio of 1:1 taking the materials, adding the materials into a mortar, and grinding for 15 minutes to ensure that the two simple substance powders are uniformly mixed. Then the powder is transferred into a porcelain boat with a cover and is moved into a quartz tube which is vacuumized (less than or equal to 200 Pa). And (3) placing the quartz tube into a tube furnace, raising the temperature to 590 ℃ by a program, keeping the temperature for 72 hours, and then naturally cooling to room temperature to obtain SnSe powder. The powder was mixed with 30 wt.% glucose and transferred to a ball mill tank under argon atmosphere (ball to feed ratio 30:1) and subjected to high energy ball milling at 350rpm for 30 min. And separating the product by using a 200-mesh sieve, placing the product into a porcelain boat after sieving, transferring the porcelain boat into a quartz tube which is introduced with an argon environment, transferring the quartz tube into a tube furnace, annealing for 5 hours at 800 ℃ in the tube furnace, cooling to room temperature, taking out the product, fully grinding the product in a mortar, and sieving by using the 200-mesh sieve to obtain the required material. In the embodiment, the ball milling condition is dry milling (no absolute ethyl alcohol is added), the glucose solubility is not required to be considered, and the operation is simple and convenient; the annealing treatment at the annealing temperature of 800 ℃ for 5 hours can obtain a reduced carbon layer with a certain graphitization degree, the effect can be achieved, and the annealing treatment at a higher temperature for a longer time can increase energy consumption and is not economical.
The button cell assembled by the negative electrode material is tested, and the cell is packaged according to the sequence of the negative electrode shell, the negative electrode plate, the glass fiber diaphragm, the sodium sheet, the gasket, the spring sheet and the positive electrode shell. The half cell test method comprises the following steps: the tin selenide composite material coated by the carbon layer, acetylene black and 3 wt.% of CMC (dissolved in deionized water) are uniformly mixed according to the proportion of 8:1:1 and stirred for 6 hours. This was then coated on copper foil and dried overnight at 80 ℃. Assembling half cell in glove box, water pressure and oxygen pressure are both lower than 0.1ppm, and electrolyte is 1M NaPF6In a solvent of EC DEC ═ 1:1 and 5 vt% FEC. The charge and discharge voltage is 0.01V-2V, and 0.1C is 70 mA/g.
An SEM image of the negative electrode material prepared in this embodiment is shown in fig. 1, a raman spectrogram is shown in fig. 2, a cyclic voltammetry curve of the assembled half-cell is shown in fig. 3, an impedance spectrum is shown in fig. 4, a charge-discharge curve is shown in fig. 5, a cyclic performance versus ratio curve is shown in fig. 6, and a rate performance comparison curve is shown in fig. 7, and it is obvious that both the cyclic stability and the rate performance of the modified negative electrode material are stably improved. Wherein the capacity retention rate after 100 cycles after modification is 85.47%, and the capacity retention rate after 100 cycles before modification is less than 10%. Because of the addition of the carbon layer coating, the rate capability is obviously improved, and the capacity can still keep a higher level under the condition of heavy current discharge.
Example 2:
se powder and Sn powder are mixed according to a molar ratio of 1:1 taking the materials, adding the materials into a mortar, and grinding for 15 minutes to ensure that the two simple substance powders are uniformly mixed. Then the powder is transferred into a porcelain boat with a cover and is moved into a quartz tube which is vacuumized (less than or equal to 200 Pa). And (3) placing the quartz tube into a tube furnace, raising the temperature to 590 ℃ by a program, keeping the temperature for 72 hours, and then naturally cooling to room temperature to obtain SnSe powder. The powder was mixed with 30 wt.% glucose and transferred to a ball mill tank under argon atmosphere (ball to feed ratio 30:1) and subjected to high energy ball milling at 350rpm for 30 min. And separating the product by using a 200-mesh sieve, placing the product into a porcelain boat after sieving, transferring the porcelain boat into a quartz tube which is introduced with an argon environment, transferring the quartz tube into a tube furnace, annealing at 700 ℃ for 5 hours, cooling to room temperature, taking out the quartz tube, fully grinding the quartz tube in a mortar, and then sieving by using a 200-mesh sieve to obtain the required material. The obtained material was subjected to half-cell assembly and testing to obtain fig. 8, the first discharge specific capacity was 688.24mAh/g, the remaining specific capacity after 100 cycles was 559.73mAh/g, and the capacity retention rate after 100 cycles was 81.32%.
Example 3:
se powder and Sn powder are mixed according to a molar ratio of 1:1 taking the materials, adding the materials into a mortar, and grinding for 15 minutes to ensure that the two simple substance powders are uniformly mixed. Then the powder is transferred into a porcelain boat with a cover and is moved into a quartz tube which is vacuumized (less than or equal to 200 Pa). And (3) placing the quartz tube into a tube furnace, raising the temperature to 590 ℃ by a program, keeping the temperature for 72 hours, and then naturally cooling to room temperature to obtain SnSe powder. The powder was mixed with 30 wt.% phenolic resin and mixed with 7.5ml absolute ethanol and transferred to a ball mill pot under argon atmosphere (ball to feed ratio 30:1) and subjected to high energy ball milling at 350rpm for 30 min. And (3) drying the product in vacuum at 80 ℃ for 2 hours, separating by using a 200-mesh sieve, placing the product in a porcelain boat after sieving, transferring the product into a quartz tube which is introduced with argon atmosphere, transferring the quartz tube into a tube furnace, annealing at 750 ℃ for 5 hours, cooling to room temperature, taking out the product, fully grinding the product in a mortar, and sieving by using the 200-mesh sieve to obtain the required material. The obtained material is subjected to half-cell assembly and testing to obtain a graph 9, the first discharge specific capacity is 695.36mAh/g, the residual specific capacity after 100 cycles is 561.38mAh/g, and the capacity retention rate after 100 cycles is 80.73%. In the embodiment, the absolute ethyl alcohol dissolves the phenolic resin and plays a role of a grinding aid.
Comparative example 1:
this comparative example differs from example 1 in that: the annealing temperature of this comparative example was 600 ℃. The material was tested for button cell assembly under the same conditions as in example 1. The first discharge specific capacity of the half-battery is 687.28mAh/g, the residual specific capacity after 100 cycles is 537.19mAh/g, and the capacity retention rate is 78.16%.
Comparative example 2:
this comparative example differs from example 1 in that: the material was subjected to high energy ball milling with phenol resin without absolute ethanol at 330rpm under the same conditions as in example 1. The first discharge specific capacity of the half-battery is 665.94mAh/g, the residual specific capacity after 100 cycles is 437.29mAh/g, and the capacity retention rate is 65.66%.
Claims (7)
1. A preparation method of a carbon-coated tin selenide cathode material is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: mixing Sn powder and Se powder according to the weight ratio of 1:1, transferring the mixture into a vacuum quartz tube after mixing, and performing high-temperature calcination by using a tube furnace;
step two: grinding and sieving the product SnSe powder obtained by calcining, and mixing the sieved product with a carbon source;
step three: carrying out high-energy ball milling treatment in an inert atmosphere, and screening to obtain a product;
step four: annealing treatment is carried out to form SnSe powder coated with a carbon layer on the surface.
2. The preparation method of the carbon-coated tin selenide anode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the first step, the high-temperature calcination is carried out at 590 ℃, the time is 72h, and the vacuum degree is less than or equal to 200 Pa.
3. The preparation method of the carbon-coated tin selenide anode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the second step, the mass ratio of the carbon source to the total mixture is 10-40 wt.%.
4. The preparation method of the carbon-coated tin selenide anode material as claimed in claim 1 or 3, wherein the preparation method comprises the following steps: in the second step, the carbon source is one or a combination of glucose, sucrose or phenolic resin.
5. The preparation method of the carbon-coated tin selenide anode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the third step, the rotating speed of the high-energy ball mill is 350rpm, and the time is 30 min.
6. The preparation method of the carbon-coated tin selenide anode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the fourth step, the temperature of the annealing treatment is 700-800 ℃, and the time is 3-5 hours.
7. The application of the carbon-coated tin selenide negative electrode material prepared by any one of claims 1 to 6 is characterized in that: the carbon-coated tin selenide cathode material is applied to a sodium ion battery.
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