CN109301204B - Preparation method of hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material - Google Patents

Preparation method of hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material Download PDF

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CN109301204B
CN109301204B CN201811115850.0A CN201811115850A CN109301204B CN 109301204 B CN109301204 B CN 109301204B CN 201811115850 A CN201811115850 A CN 201811115850A CN 109301204 B CN109301204 B CN 109301204B
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CN109301204A (en
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殷立雄
蔺英
程如亮
张浩繁
黄剑锋
白培杰
李慧敏
宋佳琪
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Shaanxi University of Science and Technology
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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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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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    • 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 discloses a preparation method of a hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material, which is prepared by mixing SnCl4·5H2Dissolving O in a mixed solution of deionized water and absolute ethyl alcohol to fully dissolve the O to form a solution A, and dissolving NaOH in the solution A to prepare a solution B; adding urea into the solution B under the stirring action, continuously stirring to form a uniform mixed solution C, and then carrying out a homogeneous hydrothermal reaction on the mixed solution C; after the reaction is finished, the SnO is obtained by washing and drying2A precursor; SnO2Heating and firing the precursor to obtain SnO2Powder; SnO2Dispersing the powder in ethanol and stirring to obtain a uniformly mixed suspension D; adding SnCl to suspension D4·5H2O and TAA, stirring until complete dissolution to form a uniform suspension E; and (3) carrying out microwave hydrothermal reaction on the suspension E, taking out a product after the reaction is finished, and washing and drying to obtain the hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material.

Description

Preparation method of hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material
Technical Field
The invention relates to a preparation method of a lithium ion battery cathode material, in particular to a preparation method of a hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material.
Background
With the popularization of various high-tech portable electronic products such as mobile phones, digital cameras, notebook computers and the like as people enter the information-oriented society, the demand of people for safe and high-performance portable small power supplies is rapidly increased. The lithium ion battery is a novel chemical power supply, and meets the application requirements of electronic products, such as small volume, light weight, high energy density, long cycle life, good safety performance, rapid charge and discharge, and the like, so that the lithium ion battery becomes a hotspot of current research and application. There are still many problems to be solved, such as: the high cost, capacity requirements and cycle performance are insufficient, which makes the development of suitable battery materials important.
SnS2Is a binary compound belonging to the IV: VI main group and is composed of hexagonal basic units CdI2The layered crystal structure (unit cell parameters: a: 0.3648nm, c: 0.5899nm) is composed of a sandwich structure (S-Sn-S) of two layers of hexagonally close-packed sulfide ions with tin ions added in the middle. One tin ion is inserted into every six sulfide ions to form a regular octahedral coordination, and weak van der waals forces exist between layers and are bound by covalent bonds. In addition, the layered structure has many crystal vacancies, which can be used as the host lattice of intercalation. The unique properties of these different structures are utilized to prepare semiconductor materials, photocatalytic materials, solar cell materials, photoelectric conversion system materials, lithium ion battery materials, and the like. Unique performance and wide application of SnS2Materials have become one of the most promising materials. Moreover, SnS2Due to its high theoretical capacity (690 mAh. g)-1) The lithium ion battery cathode material has the advantages of abundant natural resources, no toxicity and low cost, is considered as a promising candidate of a new generation of cathode material, but has the defects of poor conductivity, large volume expansion in the charge and discharge process and the like of most cathode materials, and the development of the lithium ion battery cathode material is limited.
Nano SnO2Has the advantages ofSub-size effects and thus a wider forbidden bandwidth, and the Senthikumar et al show that nano SnO2The smaller the particle size, the larger the forbidden band width, which can be up to 4.26 eV. Because of the inherent small-size effect and surface effect of the nano material, the nano material shows special effects in the aspects of light absorption, photocatalysis, gas-sensitive response and the like, and has been widely researched and applied in the aspects of storage materials, gas-sensitive elements, photocatalysis materials, electrode materials, solar cell materials and the like. Likewise, SnO2It is also considered as a promising candidate for a new generation of anode material and has been studied extensively due to its high theoretical capacity (782mAh/g), abundant natural resources, non-toxicity and low cost. Thus, SnS2With SnO2And compounding is carried out, so that the electrochemical performance of the lithium ion battery cathode material is improved.
At present, SnS2/SnO2The preparation method mainly comprises two steps (solvothermal method and heat treatment method) [ Wang W, Xu C, Wang X, et al2 nanorods by annealing SnO2 powder in NaCl flux[J].Journal of Materials Chemistry,2002,12(6):1922-1925.]Electrospinning and heat treatment [ Li Y, Wang J G, Sun H, et al, heterogeneous SnS2/SnO2, nanotubes with enhanced charge separation and excellent photocatalytic hydrogen production [ J].International Journal of Hydrogen Energy,2018.]And the like. The solvent thermal reaction method is an improved hydrothermal reaction method, an organic solvent is used as a solvent instead of the traditional water, but the reaction process needs to strictly control the solvent thermal condition. The thermal decomposition method has simple reaction operation and high reaction speed, but is easy to cause product agglomeration, the temperature required by the reaction is higher, and the requirements on energy and cost required by production are higher. The electrostatic spinning yield is unstable, the efficiency is low, only 0.1 g/h-1 g/h can be obtained per hour, the industrialization and the scale of the electrostatic spinning are greatly hindered, the wide application of the nanofiber material is greatly hindered, and the requirement of the traditional market on the dosage of the nanofiber cannot be met.
Disclosure of Invention
The invention aims to provide a SnS with a hollow sphere structure2/SnO2Negative electrode material for lithium ion batteryThe preparation method of the material overcomes the defects in the prior art, has low preparation cost, simple operation and short preparation period, and the obtained SnS with the hollow sphere structure2/SnO2The lithium ion battery cathode material has high capacity and good cycling stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material comprises the following steps:
1) SnCl4·5H2Dissolving O in the mixed solution of deionized water and absolute ethyl alcohol to fully dissolve O to form solution A according to the mass ratio of elements mSn:mNaDissolving NaOH in the solution A to prepare a solution B, wherein (0.5-1): 0.6-0.95);
2) adding urea into the solution B under the stirring action, and continuously stirring to obtain a uniformly mixed solution C containing SnCl4·5H2The mass ratio of O to urea is (0.5-1): (0.3-0.7), and then carrying out homogeneous hydrothermal reaction on the mixed solution C;
3) after the reaction is finished, respectively centrifugally washing the product for a plurality of times by deionized water and absolute ethyl alcohol, and then drying in vacuum to obtain SnO2A precursor;
4) SnO2Heating the precursor for 1-5 h at 300-500 ℃, controlling the heating rate at 1-5 ℃/min, and obtaining SnO when the temperature is reduced to room temperature2Powder;
5) SnO2Dispersing the powder in ethanol and stirring to obtain a uniformly mixed suspension D;
6) SnCl4·5H2O and TAA in the molar ratio of the elements nSn：nSAdding the (1-4) into the suspension D, and stirring until the suspension D is completely dissolved to form a uniform suspension E;
7) and (3) carrying out microwave hydrothermal reaction on the suspension E, taking out a product after the reaction is finished, respectively centrifugally washing the product for a plurality of times by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying to obtain the tin sulfide/tin oxide lithium ion battery cathode material with the hollow sphere structure.
Further, 0.5g to 1g of SnCl is dissolved in each 60mL of the mixed solution of the deionized water and the absolute ethyl alcohol in the step 1)4·5H2O。
Further, V in the mixed solution of the deionized water and the absolute ethyl alcohol in the step 1)Deionized water：VAnhydrous ethanol＝1:5～5:1。
Further, the step 2) of performing a homogeneous hydrothermal reaction on the mixed solution C specifically comprises: and (3) sealing the mixed solution C in a homogeneous hydrothermal reaction kettle, controlling the filling ratio to be 40% -60%, placing the mixed solution C in a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160-200 ℃ and the reaction time to be 12-30 h.
Further, the temperature of vacuum drying in the step 3) and the step 7) is 80 ℃, and the time is 12 hours.
Further, 0.25 g-0.45 g SnO is dispersed in 40-60 mL ethanol in the step 5)2And (3) powder.
Further, in the step 6), 0.5-1.5g of SnCl is added into every 40-60 mL of the suspension D4·5H2O。
Further, the microwave hydrothermal reaction of the suspension E in the step 7) is specifically as follows: and (4) putting the suspension liquid E into a microwave hydrothermal kettle, and reacting for 1-5 hours at 160-200 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
SnS with hollow sphere structure prepared by using method2/SnO2Compared with other structures, the hollow sphere structure prepared by the invention has the advantages of light weight, larger specific surface area, increased reactive active sites and the like, and is beneficial to increasing Li+Diffusion channels, Li+The migration distance of the catalyst is shortened, so that the performance of the lithium ion battery cathode material is improved, in addition, the reaction rate is high, the reaction is full and thorough, the product has strong crystallinity, special appearance, controllable grain growth and uniform size distribution, the heat loss of the traditional heating mode is eliminated, and the catalyst has the advantages of high heating speed, uniform heating, no temperature gradient and no hysteresis, andthe effect and the like, and the experimental result shows that the current is 300 mA.g-1The first discharge capacity under the current density can reach 1679.6mAh g-1The capacity is maintained at 575.6mAh g after 50 cycles of circulation-1And has good circulation stability.
Drawings
FIG. 1 is SnS prepared according to example 2 of the present invention2/SnO2XRD pattern of lithium ion battery cathode material;
FIG. 2 shows SnS with hollow sphere structure prepared in example 2 of the present invention2/SnO2SEM image of battery negative electrode material;
FIG. 3 is SnS prepared according to example 2 of the present invention2/SnO2The content of the battery negative electrode material is 300mA · g-1Current density cycling performance plot.
Detailed Description
Embodiments of the invention are described in further detail below:
1) 0.5g to 1g of SnCl4·5H2O dissolved in 60mL deionized water and absolute ethanol (V)Deionized water：VAnhydrous ethanol1:5 to 5:1) to form a solution A by dissolving the components sufficiently, wherein the mass ratio of the components m isSn:mNaDissolving NaOH in the solution A to prepare a solution B, wherein the solution B is 0.5-1 (0.6-0.95);
2) adding 0.3-0.7 g of urea into the solution B under the action of magnetic stirring, continuously stirring to form a uniformly mixed solution C, placing the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40-60%, placing into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160-200 ℃ and the reaction time to be 12-30 hours;
3) after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol to obtain a white precursor, and drying the white precursor in vacuum for 12 hours at the temperature of 80 ℃ to obtain SnO2A precursor;
4) heating the mixture in a muffle furnace for 1 to 5 hours at the temperature of between 300 and 500 ℃, controlling the heating rate to be between 1 and 5 ℃/min, opening the muffle furnace when the temperature is reduced to the room temperature, taking out the porcelain boat, and obtaining a fine powdery sample, namely SnO2Powder;
5) SnO prepared by the above steps2Weighing 0.25-0.45 g of the materials, dispersing in 40-60 ml of ethanol, and magnetically stirring for 1h to obtain a uniformly mixed suspension D;
6) adding n to the suspension according to the element molar ratioSn：nS(1-4) adding SnCl into the suspension D4·5H2Stirring O and TAA (thioacetamide) until the O and the TAA are completely dissolved to form a uniform suspension E, and adding 0.5-1.5g SnCl into every 40-60 mL of the suspension D4·5H2O；
7) And (3) putting the obtained suspension E with different tin-sulfur ratios into a microwave hydrothermal kettle, and reacting for 1-5 h at 160-200 ℃ under the microwave condition to obtain a precursor. After the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol, and drying the precursor for 12 hours in vacuum at the temperature of 80 ℃ to obtain the SnS2/SnO2And (3) precursor.
The present invention is described in further detail below with reference to examples:
example 1
1) 0.5g of SnCl4·5H2O dissolved in 60mL deionized water and absolute ethanol (V)Deionized water：VAnhydrous ethanol1:5) to form a solution a, in terms of the element mass ratio mSn:mNaDissolving NaOH in the solution A to prepare a solution B (0.5: 0.6);
2) adding 0.3g of urea into the solution B under the action of magnetic stirring, continuously stirring to form a uniform mixed solution C, placing the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40%, placing into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160 ℃ and the reaction time to be 12 hours;
3) after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol to obtain a white precursor, and drying the white precursor in vacuum for 12 hours at the temperature of 80 ℃ to obtain SnO2A precursor;
4) heating in a muffle furnace at 300 ℃ for 1h, controlling the heating rate at 1 ℃/min, opening the muffle furnace when the temperature is reduced to room temperature, taking out the porcelain boat, and obtaining a fine powdery sample, namely SnO2Powder;
5) SnO prepared by the above steps2Weighing 0.25g of the materials, dispersing in 40ml of ethanol, and magnetically stirring for 1h to obtain a uniformly mixed suspension D;
6) adding n into the suspension according to the element molar ratioSn：nS1:1 addition of SnCl to suspension D4·5H2O and TAA (thioacetamide) are stirred until complete dissolution to form a homogeneous suspension E, 0.5g of SnCl is added per 40mL of suspension D4·5H2O；
7) And (3) putting the suspension E into a microwave hydrothermal kettle, and reacting for 1h at 160 ℃ under the microwave condition to obtain a precursor. After the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol, and drying the precursor for 12 hours in vacuum at the temperature of 80 ℃ to obtain the SnS2/SnO2And (3) precursor.
Example 2
1) 0.7102g SnCl4·5H2O dissolved in 60mL deionized water and absolute ethanol (V)Deionized water：VAnhydrous ethanol1:1) to form a solution a, wherein m is the mass ratio of the elementsSn:mNaDissolving NaOH in the solution a to prepare a solution B (0.7102: 0.8002);
2) adding 0.5g of urea into the solution B under the action of magnetic stirring, continuously stirring to form a uniform mixed solution C, placing the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50%, placing into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 180 ℃ and the reaction time to be 24 hours;
3) after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol to obtain a white precursor, and drying the white precursor in vacuum for 12 hours at the temperature of 80 ℃ to obtain SnO2A precursor;
4) heating in a muffle furnace at 400 ℃ for 3h, controlling the heating rate at 2 ℃/min, opening the muffle furnace when the temperature is reduced to room temperature, taking out the porcelain boat, and obtaining a fine powdery sample, namely SnO2Powder;
5) SnO prepared by the above steps20.3104g of material is weighed and dispersed in 50Adding the mixture into ml of ethanol, and magnetically stirring for 1 hour to obtain a uniformly mixed suspension D;
6) adding n into the suspension according to the element molar ratioSn：nS1:2 addition of SnCl to suspension D4·5H2O and TAA (thioacetamide) are stirred until complete dissolution to form a homogeneous suspension E; 1.5g SnCl was added per 60mL of suspension D4·5H2O
7) And (3) putting the suspension E into a microwave hydrothermal kettle, and reacting for 3h at 180 ℃ under the microwave condition to obtain a precursor. After the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol, and drying the precursor for 12 hours in vacuum at the temperature of 80 ℃ to obtain the SnS2/SnO2And (3) precursor.
From FIG. 1, it can be seen that SnS prepared by the present embodiment2/SnO2The crystallinity is better, the purity of the product is better, and the SnS with the hollow sphere structure prepared by the embodiment can be seen from figure 22/SnO2The diameter of the battery negative electrode material is about 500nm-900 nm; as can be seen from FIG. 3, the first discharge capacity of the product prepared by the present example as the negative electrode material of the lithium ion battery can reach 1679.6mAh g-1The capacity is maintained at 575.6mAh g after 50 cycles of circulation-1And has good circulation stability.
Example 3
1) 1g of SnCl4·5H2O dissolved in 60mL deionized water and absolute ethanol (V)Deionized water：VAnhydrous ethanol5:1) to form a solution a, wherein m is the mass ratio of the elementsSn:mNaDissolving NaOH in the solution A to prepare a solution B (1: 0.95);
2) adding 0.7g of urea into the solution B under the action of magnetic stirring, continuously stirring to form a uniform mixed solution C), putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 60%, putting into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 200 ℃ and the reaction time to be 30 hours;
3) after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol to obtain a white precursor at the temperature of 80 DEG CVacuum drying for 12h to obtain SnO2And (3) precursor.
4) Heating in a muffle furnace at 500 deg.C for 5h, controlling the heating rate at 5 deg.C/min, opening the muffle furnace when the temperature is reduced to room temperature, taking out the porcelain boat, and obtaining fine powder sample, i.e. SnO2。
5) SnO prepared by the above steps2Weighing 0.45g of the materials, dispersing in 60ml of ethanol, and magnetically stirring for 1h to obtain a uniformly mixed suspension D;
6) adding n into the suspension according to the element molar ratioSn：nS1:4 to suspension D above SnCl was added4·5H2O and TAA (thioacetamide) are stirred until complete dissolution to form a homogeneous suspension E; 1g of SnCl was added to 50mL of suspension D4·5H2O
7) And (3) putting the suspension E into a microwave hydrothermal kettle, and reacting for 5 hours at 200 ℃ under the microwave condition to obtain a precursor. After the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by deionized water and absolute ethyl alcohol, and drying the precursor for 12 hours in vacuum at the temperature of 80 ℃ to obtain the SnS2/SnO2And (3) precursor.

Claims (6)

1. A preparation method of a hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material is characterized by comprising the following steps:
1) SnCl4·5H2Dissolving O in the mixed solution of deionized water and absolute ethyl alcohol to fully dissolve O to form solution A according to the mass ratio of elements mSn:mNaDissolving NaOH in the solution A to prepare a solution B, wherein (0.5-1): 0.6-0.95);
2) adding urea into the solution B under the stirring action, and continuously stirring to obtain a uniformly mixed solution C containing SnCl4·5H2The mass ratio of O to urea is (0.5-1): (0.3-0.7), then placing the mixed solution C into a homogeneous hydrothermal reaction kettle for sealing, controlling the filling ratio to be 40% -60%, placing the mixed solution C into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160-200 ℃ and the reaction time to be 12-30 h;
3) after the reaction is finished, the product is processed by deionized waterAnd absolute ethyl alcohol are respectively centrifugally washed for a plurality of times, and then vacuum drying is carried out to obtain SnO2A precursor;
4) SnO2Heating the precursor for 1-5 h at 300-500 ℃, controlling the heating rate at 1-5 ℃/min, and obtaining SnO when the temperature is reduced to room temperature2Powder;
5) SnO2Dispersing the powder in ethanol and stirring to obtain a uniformly mixed suspension D;
6) SnCl4·5H2O and TAA in the molar ratio of the elements nSn：nSAdding the suspension D into (1-4), and adding 0.5-1.5g SnCl into every 40-60 mL of the suspension D4·5H2Stirring until the mixture is completely dissolved to form a uniform suspension E;
7) and (3) carrying out microwave hydrothermal reaction on the suspension E, taking out a product after the reaction is finished, respectively centrifugally washing the product for a plurality of times by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying to obtain the tin sulfide/tin oxide lithium ion battery cathode material with the hollow sphere structure.
2. The preparation method of the hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material of claim 1, wherein 0.5g to 1g of SnCl is dissolved in 60mL of mixed solution of deionized water and absolute ethyl alcohol in the step 1)4·5H2O。
3. The preparation method of the hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material according to claim 1, wherein V in the mixed solution of deionized water and absolute ethyl alcohol in the step 1)Deionized water：VAnhydrous ethanol＝1:5～5:1。
4. The preparation method of the hollow sphere structure tin sulfide/tin oxide lithium ion battery negative electrode material according to claim 1, wherein the temperature of vacuum drying in the step 3) and the step 7) is 80 ℃ and the time is 12 hours.
5. A method as claimed in claim 1The preparation method of the hollow sphere structure tin sulfide/tin oxide lithium ion battery cathode material is characterized in that 0.25 g-0.45 g SnO is dispersed in 40-60 mL ethanol in the step 5)2And (3) powder.
6. The preparation method of the hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material according to claim 1, wherein the step 7) of performing microwave hydrothermal reaction on the suspension E specifically comprises the following steps: and (4) putting the suspension liquid E into a microwave hydrothermal kettle, and reacting for 1-5 hours at 160-200 ℃.
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