CN113772718B - SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof - Google Patents
SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses SnS-SnS 2 The @ GO heterostructure composite material and the preparation method and the application thereof, the preparation method comprises the following processes: preparing solution A, solution B and solution C: wherein the preparation process of the solution A comprises the following steps: dissolving a tin source and reducing acid in an alcohol solvent until the tin source is completely dissolved to obtain a solution A, wherein the solution A is acidic; the solution B is graphene dispersion solution, and the solution C is a solution of a sulfur source dissolved in ethylene glycol; mixing the solution A and the solution B, adding a surfactant, and uniformly mixing to obtain solution D; adding the solution C into the solution D to react tin with sulfur to obtain solution E; carrying out hydrothermal reaction on the solution E, filtering, washing and drying to obtain the SnS-SnS 2 @ GO heterostructure composite. The invention relates to SnS-SnS 2 The @ GO heterostructure composite material has the characteristics of good cycle performance and low capacity attenuation tendency.
Description
Technical Field
The invention relates to the field of new energy material preparation, in particular to SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof.
Background
Sodium ion batteries are considered as alternatives to lithium ion batteriesOne of the substitutes is mainly because more than 80 percent of lithium resources are abroad in the world in terms of lithium resource reserves, and 80 percent of lithium resources exist in salt lake brine in China, so that Mg/Li is high, and the lithium extraction technology has high cost. And at present, about 80% of lithium resources used in China come from foreign imports, so that the price of the metal lithium is rapidly increased, and a novel lithium ion battery substitute product is urgently required to be found. From the perspective of national development strategy, the development of sodium ion batteries can ensure that the development of sodium ion batteries is not influenced by resource reserves and geopolitics due to sufficient sodium resources, and the advantages of similar electrochemical principles, proper electrochemical windows and high safety and stability of the sodium ion batteries and the lithium ion batteries become a new star in the field of new energy. But do not
Ratio of
Large radius, larger ionic radius makes Na + The material is difficult to migrate in the electrochemical process, and the structure of the material is collapsed or even pulverized in the process of sodium intercalation and deintercalation, so that the problems of slow electrochemical reaction kinetics, poor reversibility and short cycle life of the sodium ion battery are caused, and the research of an excellent electrode material is particularly important for improving the energy density and the cycle performance of the sodium ion battery.
The negative electrode material of a sodium ion battery largely determines the operating voltage, capacity, rate capability and cycle performance of the battery. The carbon negative electrode material commonly used in the current market has the defects of low specific capacity, quick capacity attenuation and poor safety performance, and can not meet the development requirements of batteries with high energy storage and long service life. The SnS material is regarded as one of promising sodium ion battery cathode materials, has a higher theoretical capacity of 1022mAh/g, has a layered structure similar to graphene, is connected together through Van der Waals force, has an orthorhombic structure, and has a layered spacing of 0.43nm. This particular layered structure favors Na + Can be rapidly de-embedded during the charging and discharging process. But at electrochemistryDuring the reaction process, snS is accompanied with the desorption of sodium ions, so that the material generates larger volume change, internal stress is continuously accumulated so as to generate cracks and diffuse, further, active substances fall off from a current collector, charge transfer is damaged, the cycle performance is deteriorated, and the capacity is rapidly attenuated.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide SnS-SnS 2 The invention discloses a @ GO heterostructure composite material, a preparation method and application thereof, and relates to SnS-SnS 2 The @ GO heterostructure composite material has the characteristics of good cycle performance and low capacity attenuation tendency.
The technical scheme adopted by the invention is as follows:
SnS-SnS 2 The preparation method of the @ GO heterostructure composite material comprises the following steps:
preparing solution A, solution B and solution C: wherein the preparation process of the solution A comprises the following steps: dissolving a tin source and reducing acid in an alcohol solvent until the tin source is completely dissolved to obtain a solution A, wherein the solution A is acidic; the solution B is graphene dispersion solution, and the solution C is a solution of sulfur source dissolved in ethylene glycol;
mixing the solution A and the solution B, adding a surfactant, and uniformly mixing to obtain solution D;
adding the solution C into the solution D to react tin with sulfur to obtain solution E;
carrying out hydrothermal reaction on the solution E, filtering, washing and drying to obtain the SnS-SnS 2 @ GO heterostructure composites.
Preferably, the tin source comprises SnCl 2 ·2H 2 O、SnCl 4 ·5H 2 O、SnSO 4 Or tin acetate.
Preferably, the reducing acid comprises citric acid, ascorbic acid or oxalic acid.
Preferably, the alcoholic solvent comprises one or more of ethylene glycol, polyethylene glycol and PEG-500.
Preferably, the pH of solution A is adjusted by the reducing acid, and the pH of solution A is-1 to 0.
Preferably, the surfactant is CTAB, PVB or TAG-500.
Preferably, the hydrothermal reaction of the solution E is carried out at the reaction temperature of 140-180 ℃ for 12-36h.
Preferably, the drying temperature is 50-100 ℃, and the drying time is 8-24h.
The invention also provides SnS-SnS 2 @ GO heterostructure composites, the SnS-SnS 2 The @ GO heterostructure composite material is prepared by the preparation method disclosed by the invention, wherein the molar ratio of GO, sn and S is (0.8-1.2): (0.8-1.2): 1.
The invention also provides SnS-SnS 2 Application of @ GO heterostructure composite material and SnS-SnS 2 The @ GO heterostructure composite material is used as a sodium ion battery negative electrode material.
The invention has the following beneficial effects:
the invention can form SnS-SnS by using a one-step solvothermal method and E liquid 2 Heterostructure and SnS-SnS 2 The heterostructure is compounded with Graphene Oxide (GO) to obtain SnS-SnS 2 @ GO heterostructure composite material, nano SnS-SnS in the material 2 The particles can further prevent the particles from agglomerating and buffer the volume effect of the material. SnS-SnS 2 The heterostructure can induce an internal electric field, further generates a charge driving force, and solves the problem of low conductivity of the material. SnS-SnS 2 Compounding with Graphene Oxide (GO) with excellent conductivity can make the material have a large specific surface area and excellent mechanical flexibility, can effectively promote the transmission of electrons and ions, and can also help to alleviate the volume expansion in the process of sodium ion deintercalation effectively, maintain stable structure, and then make the reaction process GO on more quickly and smoothly.
Drawings
FIG. 1 shows that the temperature is 140 ℃ under the conditions of SnS-SnS in the embodiment of the invention 2 The XRD pattern of @ GO heterostructure composites;
FIG. 2 shows that the temperature is 140 ℃ under the conditions of SnS-SnS 2 SEM images of @ GO heterostructure composites;
FIG. 3 shows an example of the present invention at 140 deg.CSnS-SnS 2 A plot of the cyclic performance of the @ GO heterostructure composite;
FIG. 4 shows SnS-SnS at 160 deg.C in an embodiment of the present invention 2 XRD pattern of @ GO heterostructure composites
FIG. 5 shows SnS-SnS at 160 deg.C in an embodiment of the present invention 2 SEM images of @ GO heterostructure composites;
FIG. 6 shows SnS-SnS at 160 deg.C in an embodiment of the present invention 2 A plot of the cyclic performance of the @ GO heterostructure composite;
FIG. 7 shows SnS-SnS at 180 ℃ in an embodiment of the present invention 2 XRD pattern of @ GO heterostructure composite;
FIGS. 8 (a) and 8 (b) are graphs showing that SnS-SnS is shown at 180 ℃ in examples of the present invention 2 SEM images at different magnifications of @ GO heterostructure composite;
FIG. 9 shows SnS-SnS at 180 deg.C in an embodiment of the present invention 2 EDS energy spectra of @ GO heterostructure composites;
FIG. 10 shows SnS-SnS at 180 deg.C in an embodiment of the present invention 2 The cycle performance diagram of @ GO heterostructure composites.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention provides SnS-SnS 2 The material is synthesized by a one-step solvothermal method, and the preparation method has the advantages of simple preparation process, convenient operation, high yield and SnS-SnS 2 The @ GO heterostructure composite material exhibits high specific energy and excellent electrochemical performance. SnS-SnS synthesized by the invention 2 The @ GO heterostructure can be used as a negative electrode material of a sodium ion battery.
The invention relates to SnS-SnS 2 The @ GO heterostructure composite material is used as a sodium ion battery negative electrode material, and the preparation process comprises the following steps:
dissolving 4-6mmol of tin source and reducing acid in an alcohol solvent, regulating the pH value by using the reducing acid when needed, regulating the pH value to be under an acidic condition, fully stirring for a period of time to completely dissolve the tin source to obtain the tin-tin composite materialThe pH value of the mixed solution of (A) is-1 to 0. Taking 15-30ml of a commercially available graphene solution, and performing ultrasonic dispersion for a period of time to obtain a graphene dispersion liquid, wherein the graphene dispersion liquid is used as a liquid B. Wherein the alcohol solvent is one or more of ethylene glycol, polyethylene glycol and PEG-500; the tin source adopts SnCl 2 ·2H 2 O、SnCl 4 ·5H 2 O、SnSO 4 Or tin acetate; the reducing acid is citric acid, ascorbic acid or oxalic acid.
And (2) dissolving 4-6mmol of sulfur source in the ethylene glycol solution to obtain solution C. Wherein the sulfur source is sodium sulfide, ammonium sulfide, thioacetamide or thiourea.
And (3) mixing the solution A and the solution B, adding a surfactant, stirring for a period of time to uniformly mix the solution A, the solution B and the surfactant to obtain a solution D, then adding the solution C into the solution D, stirring for a period of time to allow tin and sulfur to fully react and be fully mixed, then performing ultrasonic dispersion for a period of time to further promote uniform mixing, then adding the whole mixed solution system into a solvothermal kettle, reacting for a period of time at 140-180 ℃ to allow materials to fully react, and then filtering to obtain a gray-black precipitate. Wherein the surfactant is CTAB, PVB or TAG-500.
And (4) fully washing the obtained gray black precipitate, adding the gray black precipitate into a vacuum drying oven, and drying the gray black precipitate for 8 to 24 hours at the temperature of between 50 and 100 ℃ to obtain the SnS-SnS 2 @ GO heterostructure composites, snS-SnS 2 In the @ GO heterostructure composite material, the mole ratio of GO, sn and S is (0.8-1.2): (0.8-1.2): 1.
in conclusion, the invention utilizes the one-step solvothermal method to prepare the SnS-SnS 2 @ GO heterostructure composite: first, a reaction system in a solution is heated in a sealed container to generate a high-temperature and high-pressure reaction environment, so that crystals of the material grow to form a specific nanostructure. Generally, the generated product has higher purity, good crystallinity and higher yield, and the shape and the crystal growth characteristics of the product are controlled by adjusting various reaction parameters to ensure that the product forms a nano structure with special shape and crystal structure, namely nano SnS-SnS 2 Particle energyCan further prevent the particles from agglomerating and buffer the volume effect of the material. Second SnS-SnS 2 The heterostructure can induce an internal electric field, further generate a charge driving force, and solve the problem of low material conductivity. Finally, compounding with Graphene Oxide (GO) with excellent conductivity can enable the material to have larger specific surface area and excellent mechanical flexibility, can effectively promote the transmission of electrons and ions, can also effectively help to relieve the volume expansion in the process of sodium ion deintercalation, maintains stable structure, and then enables the reaction process to be carried out more quickly and smoothly. Compared with the traditional method, the method has the advantages of simple process flow and convenient operation, and can avoid secondary pollution of materials to the environment. In the experimental process, alcohol solution is selected as solvent to avoid SnCl 2 ·2H 2 Hydrolyzing O, and promoting SnS-SnS by adjusting the pH value of the mixed solution 2 Production of @ GO heterostructure composite material, reaction in combination with graphene solution at high temperature, and finally preparation of SnS-SnS by one-step solvothermal method 2 @ GO heterostructure composite.
Example 1:
this example SnS-SnS 2 The preparation process of the @ GO heterostructure composite material comprises the following steps:
respectively measuring 20ml of mixed solution of ethylene glycol and 20ml of PEG-500 as a solvent in the step (1), stirring for 60 minutes, and carrying out ultrasonic dispersion for 30 minutes, wherein 4mmol of SnCl 2 ·2H 2 O and 5mmol of citric acid were added to the solution while controlling the pH at-1 to 0, and stirred for 60 minutes to obtain solution A. 16ml of a commercially available graphene solution having a concentration of 2mg/ml was measured out and ultrasonically dispersed for 1 hour to obtain a B solution.
And (2) weighing 5mmol of thioacetamide and dissolving the thioacetamide in 10ml of ethylene glycol solution to obtain solution C.
And (3) mixing the solution A and the solution B to obtain solution D, stirring for 30 minutes, adding the solution C, stirring for 30 minutes, ultrasonically dispersing for 30 minutes, adding the solution into a solvent hot kettle, reacting for 24 hours at 140 ℃, and filtering to obtain a gray-black precipitate.
Fully washing the obtained gray black precipitate, and adding the gray black precipitate into a vacuum drying ovenDrying at 60 deg.C for 12 hr to obtain SnS-SnS 2 @ GO heterostructure composites. And weighing the prepared active material, the conductive carbon black and the binder according to the mass ratio of 7. Firstly, grinding and uniformly mixing an active material, conductive carbon black and a binder in a mortar, and then dropwise adding an NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and putting the coated battery pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. And cutting the dried pole piece into a small 12mm round pole piece. And (3) preparing a sodium ion battery, namely assembling a CR2032 type button experimental battery in a glove box filled with argon by using a metal sodium sheet as a counter electrode, using a glass fiber type as a diaphragm and using 1.0M NaCF3SO3-DEGDME as electrolyte.
SnS-SnS made from example 1 2 After analysis of the @ GO heterostructure composite, it was found that by XRD analysis, and as can be seen from FIG. 1, snS-SnS was prepared at 140 ℃ 2 @ GO heterostructure composite with SnS and SnS 2 Peaks of three phases, and for SnS, diffraction peaks appear at 2 θ =22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 °, corresponding to the (011), (012), (102), (110), (111), (013), (004), (113) crystal planes, respectively. For SnS 2 Diffraction peaks appear at 2 theta =15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 ° and 54.9 °, and corresponding crystal planes are (001), (100), (002), (101), (102), (110), (111) and (103), so that the SnS-SnS can be successfully prepared by a one-step solvothermal method 2 Heterostructure, as can be seen from FIG. 2, snS-SnS can be found by SEM analysis 2 The @ GO heterostructure composite material is integrally of a sheet structure and stacked together, and the sheet structure is generally small in diameter and is in the range of 1-10 mu m. Then, as can be seen from FIG. 3, the specific discharge capacity of the first coil of the material is 309.5mAh g -1 The coulombic efficiency of the first circle is 50.5 percent, and the capacity reaches 277.5mAh g after 50 circles of circulation -1 。
Example 2:
this example SnS-SnS 2 The preparation process of the @ GO heterostructure composite material comprises the following steps:
step (1) respectivelyA mixed solution of 20ml of ethylene glycol and 20ml of PEG-500 was measured as a solvent, stirred for 60 minutes, and ultrasonically dispersed for 30 minutes, 5mmol of SnCl 2 ·2H 2 O and 5mmol of citric acid were added to the solution while controlling the pH at-1 to 0, and stirred for 60 minutes to obtain solution A. A commercially available graphene solution having a concentration of 2mg/ml was measured at 20ml, and ultrasonically dispersed for 2 hours to obtain a B solution.
Step (2) weighing 5mmol thioacetamide and dissolving in 20ml glycol solution to obtain solution C.
And (3) mixing the solution A and the solution B to obtain solution D, stirring for 30 minutes, adding the solution C, stirring for 30 minutes, ultrasonically dispersing for 30 minutes, adding into a solvent hot kettle, reacting for 24 hours at 160 ℃, and filtering to obtain a gray-black precipitate.
And (4) fully washing the obtained gray black precipitate, adding the gray black precipitate into a vacuum drying oven, and drying the gray black precipitate for 12 hours at the temperature of 60 ℃ to obtain SnS-SnS 2 @ GO heterostructure composite. Weighing the prepared active material, conductive carbon black and binder according to the mass ratio of 7. Firstly, grinding and uniformly mixing an active material, conductive carbon black and a binder in a mortar, and then dropwise adding an NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and putting the coated battery pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 60 ℃. And cutting the dried pole piece into a small 12mm round pole piece. And (3) preparing a sodium ion battery, namely assembling a CR2032 type button experimental battery in a glove box filled with argon by using a metal sodium sheet as a counter electrode, using a glass fiber type as a diaphragm and using 1.0M NaCF3SO3-DEGDME as electrolyte.
SnS-SnS prepared according to example 2 2 @ GO heterostructure composite As can be seen from FIG. 4, snS-SnS prepared at 160 deg.C 2 @ GO heterostructure composites with SnS and SnS 2 Peaks of the two phases, and for SnS, diffraction peaks appear at 2 θ =22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 °, corresponding to the (011), (012), (102), (110), (111), (013), (004), (113) crystal planes, respectively. For SnS 2 Diffraction peaks appear at 2 theta =15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 °, and 54.9 °, respectively corresponding crystal planesThe SnS-SnS is successfully prepared by a one-step solvothermal method from (001), (100), (002), (101), (102), (110), (111) and (103) 2 The heterostructure, and with reference to FIG. 5, shows SnS-SnS in SEM image 2 The whole composite material with the @ GO heterostructure is of a sheet structure and is stacked together, the sizes of the materials are different, the diameter range is kept within the range of 500nm-5 microns, and the comparison shows that when the temperature is increased to 160 ℃, the whole size of the composite material is reduced, so that the volume effect can be further prevented, and the circulation stability of the material is ensured. Then, as can be seen from FIG. 6, the specific discharge capacity of the first coil of the material is 448.5mAh g -1 The coulombic efficiency of the first circle is 53.1 percent, and the capacity is attenuated to 302.8mAh g after 50 circles of circulation -1 The capacity retention ratio was 51.5%. By comparison with the composite material prepared in example 1, it was found that the attenuation of the capacity of the material was improved and the specific capacity of the material as a whole was increased. The specific reason is as follows: the heterostructure composite material is prepared at 160 ℃, and purer SnS-SnS can be produced 2 And the graphene oxide can be better compounded with a heterostructure under the solvothermal reaction at 160 ℃, and is SnS-SnS 2 The capacity of the heterostructure is improved, the volume effect of the heterostructure is improved, and the circulation stability of the material is guaranteed.
Example 3:
this example SnS-SnS 2 The preparation process of the @ GO heterostructure composite material comprises the following steps:
respectively measuring a mixed solution of 20ml of ethylene glycol and 20ml of PEG-500 as a solvent in the step (1), stirring for 60 minutes, and performing ultrasonic dispersion for 30 minutes, wherein 6mmol of SnCl 2 ·2H 2 O and 5mmol of citric acid were added to the solution, and the solution was stirred for 60 minutes while controlling the pH in the range of-1 to 0 to obtain solution A. A commercially available graphene solution at a concentration of 2mg/ml was measured out at 24ml, and ultrasonically dispersed for 1.5 hours as a B solution.
Step (2) weighing 5mmol thioacetamide and dissolving in 20ml glycol solution to obtain solution C.
And (3) mixing the solution A and the solution B to obtain solution D, stirring for 30 minutes, adding the solution C, stirring for 30 minutes, ultrasonically dispersing for 30 minutes, adding into a solvent thermal kettle, reacting for 24 hours at 180 ℃, and filtering to obtain a gray-black precipitate.
And (4) fully washing the obtained gray black precipitate, and adding the gray black precipitate into a vacuum drying oven to dry for 12 hours at the temperature of 60 ℃ to obtain SnS-SnS 2 @ GO heterostructure composites. Weighing the prepared active material, conductive carbon black and binder according to the mass ratio of 7. Firstly, grinding and uniformly mixing an active material, conductive carbon black and a binder in a mortar, and then dropwise adding an NMP solution to prepare slurry. And uniformly coating the obtained slurry on a copper foil, and drying the coated battery pole piece in a vacuum drying oven at 60 ℃ for 12 hours. And cutting the dried pole piece into a small 12mm round pole piece. And (3) preparing a sodium ion battery, namely assembling a CR2032 type button experimental battery in a glove box filled with argon by using a metal sodium sheet as a counter electrode, using a glass fiber type as a diaphragm and using 1.0M NaCF3SO3-DEGDME as electrolyte.
SnS-SnS made according to example 3 2 @ GO heterostructure composite material, as can be seen from FIG. 7, snS-SnS prepared at 180 DEG C 2 @ GO heterostructure composite, peaks of two phases of SnS and SnS2 are present, and for SnS, diffraction peaks appear at 2 θ =22.1 °, 26.1 °, 27.5 °, 30.5 °, 31.6 °, 31.7 °, 32 °, 39.4 ° corresponding to the (011), (012), (102), (110), (111), (013), (004), (113) crystal planes, respectively. For SnS 2 Diffraction peaks appear at 2 theta =15 °, 28.3 °, 30.6 °, 32.1 °, 41.9 °, 52.4 ° and 54.9 °, and corresponding crystal planes are (001), (100), (002), (101), (102), (110), (111) and (103), which indicates that the SnS-SnS can be successfully prepared at 180 DEG C 2 Heterostructure material, and as can be seen from FIGS. 8 (a) and 8 (b), after SEM analysis, snS-SnS 2 The @ GO heterostructure composite material is integrally of a sheet structure and is stacked together, and then is found according to figure 9 after EDS (electron spectroscopy) analysis, the composite material is found to be composed of C, S and Sn elements, and the combination of XRD analysis shows that the SnS-SnS is successfully prepared 2 @ GO heterostructure composites. As can be seen from FIG. 10, the specific discharge capacity of the first coil of the material is 528.7mAh g -1 First turn coulombic efficiency 66.27%, 50 turns passedAfter circulation, the capacity reaches 402.9mAh g -1 The capacity retention rate was 69.9%. By comparison with the composite material prepared in example 2, it was found that after 50 cycles of the material, no significant attenuation of the material capacity occurred and the overall specific capacity of the material was increased. The specific reason is as follows: the heterostructure composite material is prepared at 180 ℃, and purer SnS-SnS can be produced 2 Heterostructure to Graphite Oxide (GO) can be better with heterostructure recombination under 180 ℃ solvothermal reaction, and graphite oxide's structural stability is better, has guaranteed the stability of material.
The invention has the following advantages and technical effects:
1. SnS-SnS prepared by the invention 2 The @ GO heterostructure composite material has the characteristics of nanometer scale, high purity and special appearance; the ultrathin SnS nanosheet can be Na + Providing a larger electrolyte/electrode contact area and a shorter diffusion path;
2. according to the invention, GO is used as a carbon source, so that nanoscale composite coating of the carbon material is realized. SnS crystals grow in situ on the carbon material in the solvothermal process, and compared with the traditional method, the SnS-SnS synthesized by the method 2 The @ GO heterostructure composite material has more stable cycle performance, effectively relieves the volume effect of the material, induces an internal electric field, promotes charge transfer, improves the electronic and ionic conductivity of the material, and finally improves the electrochemical performance of the material, so the SnS-SnS synthesized by the method 2 The @ GO heterostructure composite material is made into a sodium ion battery electrode and shows high cycle stability;
3. the material obtained by the invention is prepared by a one-step solvothermal method, and has the advantages of simple process, low cost, environmental friendliness and high yield.
Specific embodiments of the present invention have been described above in detail. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logic analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention should be within the scope of the claims of the present invention.
Claims (5)
1. SnS-SnS 2 A preparation method of the @ GO heterostructure composite material is characterized by comprising the following steps:
mixing the solution A and the solution B, adding a surfactant, and uniformly mixing to obtain solution D;
adding the solution C into the solution D to react tin with sulfur to obtain solution E;
carrying out hydrothermal reaction on the solution E, filtering, washing and drying to obtain the SnS-SnS 2 @ GO heterostructure composite;
wherein the preparation process of the solution A comprises the following steps: dissolving a tin source and reducing acid in an alcohol solvent until the tin source is completely dissolved to obtain a solution A, wherein the solution A is acidic; the solution B is graphene dispersion solution, and the solution C is solution obtained by dissolving a sulfur source in ethylene glycol;
the reducing acid comprises citric acid;
the alcohol solvent comprises one or more of ethylene glycol, polyethylene glycol and PEG-500;
adjusting the pH value of the solution A by the reducing acid, wherein the pH value of the solution A is-1 to 0;
CTAB is adopted as a surfactant;
and carrying out hydrothermal reaction on the solution E, wherein the reaction temperature is 140-180 ℃, and the reaction time is 12-36h.
2. The SnS-SnS of claim 1 2 The preparation method of the @ GO heterostructure composite material is characterized in that the tin source comprises SnCl 2 ·2H 2 O、SnCl 4 ·5H 2 O、SnSO 4 Or tin acetate.
3. SnS-SnS according to claim 1 2 The preparation method of the @ GO heterostructure composite material is characterized in that the drying temperature is 50-100 ℃, and the drying time is 8-24h.
4. SnS-SnS 2 @ GO heterostructure composites, process for their preparation and their useCharacterized in that the SnS-SnS 2 @ GO heterostructure composite material prepared by the preparation method of any of claims 1 to 3, wherein the molar ratio of GO, sn and S is (0.8-1.2): (0.8-1.2): 1.
5. an SnS-SnS of claim 4 2 Application of @ GO heterostructure composite material, characterized in that the SnS-SnS 2 The @ GO heterostructure composite material is used as a sodium ion battery negative electrode material.
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