CN113675382A - Sn/MoS2@ C composite material and preparation method and application thereof - Google Patents
Sn/MoS2@ C composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses Sn/MoS2The @ C composite material is of a double-layer hollow sphere structure and comprises an inner hollow sphere and an outer sphere shell wrapping the inner hollow sphere, and the inner hollow sphere and the outer sphere areThere is a gap between the shells, wherein the inner hollow sphere is Sn/MoS2The outer layer of spherical shell is hollow mesoporous carbon spheres. The preparation method comprises the following steps: the hollow mesoporous carbon spheres are used as a reaction container, and are absorbed by capillary action to form SnO2Granules, then high temperature sulfidation to form SnS2/MoS2The composite material is finally reduced into Sn elementary substance by heat, and the metal Sn is welded with MoS with a sheet structure in a liquid state2Forming a hollow sphere structure, and forming a double-layer hollow sphere structure with the external hollow mesoporous carbon spheres. The Sn/MoS with the double-layer hollow sphere structure and good appearance is obtained by the method2The @ C composite material is applied to a negative electrode material in a lithium ion battery, so that the capacity of the battery is improved, and the stable structure enables an active material to be effectively protected in large current and long circulation.
Description
Technical Field
The invention relates to a lithium ion battery cathode material, in particular to Sn/MoS2The @ C composite material and the preparation method and the application thereof.
Background
The lithium ion battery has the characteristics of high energy density, long service life and environmental friendliness, so that the lithium ion battery is widely applied to the field of consumer electronics. The cathode material is one of the core materials of the lithium ion battery and plays an important role in the new energy lithium ion battery. Graphite negative electrode materials are widely used as the negative electrode materials of the lithium ion battery at present, and although the graphite negative electrode has long cycle life and rich raw materials and is successful on a small lithium battery, the theoretical specific capacity (372mA h g) is high-1) Lower. When the lithium ion battery is developed towards a large energy storage battery and a power battery, the problem of insufficient lithium storage capacity of the graphite cathode is further highlighted. High capacity MoS2Research on negative electrode materials is one of the most active plates of current lithium ion batteries. However, MoS2The negative electrode material also has some defects, such as poor conductivity, easy agglomeration, volume expansion in the charge-discharge process and the like which restrict MoS2The cathode material is widely applied to lithium ion batteries. The metal Sn has high theoretical specific capacity (997mA h g) as the lithium ion negative electrode material-1) Good safety, convenient synthesis, low cost, etc., and is considered to have good commercial propertiesThe lithium ion battery cathode material has promising future. However, Sn forms Li4Sn alloy in the lithium ion reversible reaction process, and the obvious volume change is easy to cause electrode deformation, splitting and pulverization, so that the electrode is failed, and the cycle life and the safety characteristic of the battery are seriously influenced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide Sn/MoS with a double-layer hollow sphere structure, which has high specific capacity, large specific surface area and good cycling stability2@ C composite material; another object of the present invention is to provide a Sn/MoS2A preparation method of the @ C composite material; another object of the present invention is to provide a Sn/MoS2Application of the @ C composite material.
The technical scheme is as follows: Sn/MoS of the invention2@ C composite material, the composite material is double-layer hollow sphere structure, and is composed of an internal hollow sphere and an outer spherical shell wrapping the internal hollow sphere, a gap exists between the internal hollow sphere and the outer spherical shell, and the internal hollow sphere is Sn/MoS2The outer layer of spherical shell is hollow mesoporous carbon spheres.
Preferably, the inner hollow sphere is MoS bonded by Sn nanoparticles2The nano-sheets are assembled, the diameter of the spherical shell of the internal hollow sphere is 100-150 nm, and the thickness of the spherical shell is 10-15 nm.
The above Sn/MoS2The preparation method of the @ C composite material comprises the following steps:
(1) dissolving potassium stannate trihydrate and urea in a mixed solvent of water and ethanol, adding hollow mesoporous carbon spheres to obtain a mixed material, vacuumizing, calcining the mixed material in an argon atmosphere for reaction, and obtaining SnO after the reaction is finished2@C；
(2) Dissolving ammonium molybdate tetrahydrate in mixed solvent of water and ethanol, adding SnO2@ C to obtain a mixed material, then vacuumizing, adding sulfur powder into the mixed material, and carrying out calcination reaction under the argon atmosphere, and after the reaction is finished, SnS2/MoS2@C；
(3)SnS2/MoS2Calcining at @ C in argon-hydrogen mixed atmosphere to obtain Sn/MoS2@ C composite material.
The tin source precursor is potassium stannate trihydrate, and is adsorbed into the hollow mesoporous carbon spheres, and then the molybdenum source precursor is adsorbed into the tin dioxide @ hollow mesoporous carbon spheres through capillary action. Taking sulfur powder as a sulfur source, carrying out vulcanization, and finally reducing the sulfur powder into a Sn simple substance at high temperature. Due to the fact that the melting point of Sn is low, the molybdenum disulfide nanosheets are combined into hollow spheres in a molten state, and the hollow spheres and the hollow mesoporous carbon spheres form a double hollow sphere structure.
Preferably, in the step (1), the mass ratio of the potassium stannate trihydrate, the urea and the hollow mesoporous carbon spheres is 1: 0.5-1: 0.1-0.2.
Preferably, in the step (1) and/or (2), the vacuumizing time is 5-10min, and the system pressure is 20-40kPa
Preferably, in the step (1), the calcination temperature is 100-200 ℃, the heating rate is 2-10 ℃/min, and the calcination time is 4-8 h.
Preferably, in step (2), ammonium molybdate tetrahydrate, sulfur powder and SnO2The mass ratio of the @ C balls is 1: 1-2: 0.5-1.
Preferably, in the step (2), the calcination temperature is 600-800 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 1-4 h.
Preferably, in the step (3), the volume content of hydrogen in the argon and hydrogen mixed atmosphere is 5%; the calcination temperature is 600-800 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 1-4 h.
The above Sn/MoS2The application of the @ C composite material as a lithium ion battery negative electrode material. Mixing Sn/MoS2The @ C, the acetylene black and the PVDF are uniformly mixed according to the mass ratio of 8: 1, and are uniformly coated on the copper foil to prepare the lithium ion battery cathode material.
Sn/MoS2The @ C composite material is used as a lithium ion battery negative electrode material, can carry out lithium intercalation/deintercalation reaction through three mechanisms simultaneously, and comprises an intercalation mechanism of a carbon material, alloying lithium intercalation of metal Sn and MoS2The transformation reaction of (3) intercalates lithium. In the charging and discharging process, a plurality of charging and discharging platforms are formed by utilizing different charging and discharging potentials of two materials, so that the specific capacity is improved. The unique structure of the double spherical shell increases the specific surface area and the ion transmission rate, and is internalThe cavity of the part provides a sufficient buffer space for the expansion of the material during charging and discharging. Based on the above characteristics, Sn/MoS2When the @ hollow mesoporous carbon sphere double-layer hollow sphere structure is applied to a lithium ion battery, the rate capability and the cycle life of the battery are remarkably enhanced.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the composite material has large specific capacity and high lithium storage performance, takes the hollow carbon spheres as a matrix and takes MoS as2And the Sn material and the carbon spheres are simultaneously limited in the carbon spheres, so that a synergistic effect is exerted, and the capacity of the battery is improved.
(2) The specific surface area of the composite material is large, and the Sn nano particles are bonded with MoS due to the unique double hollow sphere structure2The nanosheets are assembled into the hollow spheres, so that the specific surface area of the material is increased, the electrolyte is favorably permeated, and the migration rate of electrons and ions is increased.
(3) The composite material has high cycling stability, the space inside the double-layer hollow sphere can buffer the volume effect in the lithium intercalation/deintercalation process, the stability of the structure in the cycling process is facilitated, and the active material is effectively protected in large current and long cycle.
Drawings
FIG. 1 shows Sn/MoS prepared in example 22XRD contrast patterns of @ C composite and simple substance;
FIG. 2 is a transmission electron micrograph of hollow mesoporous carbon spheres used in example 2 at different magnifications;
FIG. 3 is a particulate SnO prepared in example 22Transmission electron micrographs of @ C composite;
FIG. 4 shows Sn/MoS prepared in example 22Transmission electron micrographs of @ C composite;
FIG. 5 shows Sn/MoS prepared in example 22An elemental analysis energy spectrogram of the @ C composite material;
FIG. 6 shows Sn/MoS at different temperature gradients2The XRD pattern of the evolution process of @ C composite;
FIG. 7 is a Sn/MoS alloy prepared in comparative example 12Transmission electron micrographs of the/C composite;
FIG. 8 is a graph comparing lithium storage performance tests of examples 1-2 and comparative examples 1-2;
FIG. 9 is a graph comparing lithium storage performance tests of example 2 and comparative examples 3 to 6.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
Preparing the hollow mesoporous carbon nanospheres: sequentially adding 50mL of absolute ethyl alcohol, 5mL of deionized water and 1mL of ammonia water into a beaker, adding 0.4mL of tetraethyl orthosilicate under vigorous stirring, weighing 0.2g of resorcinol and 0.2mL of formaldehyde, sequentially adding the resorcinol and the formaldehyde into the mixed solution, and magnetically stirring for 24 hours at the water bath temperature of 30 ℃. And after the reaction is finished, centrifugally washing to obtain a solid phase, drying, calcining the dried product at the high temperature of 600 ℃ for 5h at the heating rate of 2 ℃/min under the protection of argon, and then etching the product after high-temperature calcination for 12h by using 1M sodium hydroxide solution under the water bath condition of 60 ℃. And finally, centrifugally washing and drying the etched product to obtain the hollow mesoporous carbon spheres. The particle size of the obtained hollow mesoporous carbon sphere is 420nm, and the wall thickness is 25 nm.
Sn/MoS with double-layer hollow sphere structure2Preparation of @ C composite: (1) weighing 0.05g of potassium stannate trihydrate, dissolving the potassium stannate trihydrate in a mixed solvent of 2mL of water and 4mL of ethanol, adding 50mg of urea and 10mg of hollow mesoporous carbon spheres under vigorous stirring, vacuumizing for 5min, and adsorbing the potassium stannate trihydrate into the hollow mesoporous carbon spheres under the system pressure of 40 kPa. Heating the mixture for 4 hours at 100 ℃ in a tubular furnace under the argon atmosphere, and naturally cooling the mixture to room temperature after the reaction is finished to obtain tin dioxide @ hollow mesoporous carbon spheres;
(2) dissolving 0.05g of ammonium molybdate tetrahydrate in a mixed solvent of 2mL of water and 2mL of ethanol, adding 25mg of tin dioxide @ hollow mesoporous carbon spheres under vigorous stirring, vacuumizing for 5min at the system pressure of 40kPa, adsorbing the tin dioxide @ hollow mesoporous carbon spheres by capillary action, centrifuging and drying. 0.05g of sulfur powder was weighed, and the resulting composite material and sulfur powder were placed on both sides of a quartz boat, which was then heated to 300 ℃ in Ar. Keeping the reaction solution in a high-purity argon atmosphere for 1h to obtain tin disulfide/molybdenum disulfide @ hollow mesoporous carbon spheres;
(3) calcining the prepared tin disulfide/molybdenum disulfide @ hollow mesoporous carbon sphere material in a tubular furnace with 5% hydrogen content in argon-hydrogen mixed gas at 500 ℃ for 4h, and heating at the rate of 1 ℃/min to obtain Sn/MoS with a double-layer hollow sphere structure2@ C composite material.
Sn/MoS2/C, preparation and electrochemical performance analysis of the composite material negative electrode: mixing Sn/MoS2The method comprises the following steps of uniformly mixing and uniformly coating @ C, acetylene black and PVDF on copper foil in a mass ratio of 8: 1 to obtain a negative electrode material, assembling a CR2025 type button cell in a glove box filled with argon by using a lithium sheet as a counter electrode, 1mol/L LiPF 6/ethylene carbonate + dimethyl carbonate + diethyl carbonate as electrolyte and a microporous polypropylene film as a diaphragm, and testing the performance of the button cell under a current density of 1.0A g-1, wherein the results are shown in fig. 8 and 9.
Example 2
The preparation steps of the hollow mesoporous carbon nanospheres are the same as in example 1.
Sn/MoS with double-layer hollow sphere structure2Preparation of @ C composite: (1) 0.05g of potassium stannate trihydrate is weighed and dissolved in a mixed solvent of 2mL of water and 2mL of ethanol, 25mg of urea and 5mg of hollow mesoporous carbon spheres are added under vigorous stirring, and the mixture is vacuumized for 10min, and the system pressure is 20 kPa. Absorbing potassium stannate trihydrate into the hollow mesoporous carbon spheres. Heating the mixture for 8 hours at 200 ℃ in a tube furnace under the atmosphere of argon, and naturally cooling the mixture to room temperature after the reaction is finished to obtain the stannic oxide @ hollow mesoporous carbon spheres (SnO)2@C)；
(2) Dissolving 0.05g of ammonium molybdate tetrahydrate in a mixed solvent of 2mL of water and 2mL of ethanol, adding 50mg of tin dioxide @ hollow mesoporous carbon spheres under vigorous stirring, vacuumizing for 10min at the system pressure of 20kPa, adsorbing the tin dioxide @ hollow mesoporous carbon spheres by capillary action, centrifuging and drying. 0.1g of sulfur powder was weighed, and the resulting composite material and sulfur powder were placed on both sides of a quartz boat, which was then heated to 500 ℃ in Ar. Keeping the reaction solution in a high-purity argon atmosphere for 4 hours to obtain tin disulfide/molybdenum disulfide @ hollow mesoporous carbon spheres;
(3) the prepared tin disulfide/molybdenum disulfide @ hollow mesoporous carbonCalcining the ball material in a tubular furnace with 5% hydrogen content in argon-hydrogen mixed gas at 800 ℃ for 1h at the heating rate of 10 ℃/min to obtain Sn/MoS with a double-layer hollow ball structure2@ C composite material.
The hollow mesoporous carbon spheres and SnO obtained in the example2@ C Transmission Electron Microscopy (TEM) analysis was performed to obtain TEM images as shown in FIGS. 2 and 3, respectively. As can be seen from FIG. 2, the hollow mesoporous carbon spheres have good morphology, are hollow spheres with the diameter of 400-450nm, and have mesopores on the surface; as can be seen from FIG. 3, SnO is distributed in the hollow mesoporous carbon spheres2Particles, and gaps exist among the particles.
For the Sn/MoS obtained in this example2@ C composite material, Sn simple substance and MoS2XRD analysis was carried out, and the XRD contrast pattern obtained is shown in FIG. 1, from which it can be seen that peaks on the pattern and JCPDS standard card (PDF #04-0673) and MoS of tetragonal phase Sn2The JCPDS standard card (PDF #37-1492) proves that the substance contains simple substance Sn and MoS2Is present.
For Sn/MoS2TEM analysis and elemental spectroscopy at @ C, and the TEM and elemental spectroscopy spectra obtained are shown in FIGS. 4 and 5, and it is clear from FIG. 4 that reduced Sn and MoS2The nanosheets are assembled into hollow spheres, fig. 5 is a combined diagram of elements C, N, Sn, Mo and S in sequence, and as can be seen from fig. 5, the element Sn, the element Mo and the element S are distributed in the carbon spheres to form the hollow spheres, and a certain gap exists between the hollow spheres and the shell, which is consistent with the result obtained by the TEM image.
At different temperatures, for Sn/MoS2In the XRD measurement at @ C, the XRD pattern obtained is shown in FIG. 6, and it is understood from the pattern that the reduced state of the substance changes with the increase in temperature.
Sn/MoS2/C, preparation and electrochemical performance analysis of the composite material negative electrode: the preparation and analysis steps were the same as in example 1, and the results are shown in FIG. 8.
Comparative example 1
1. The preparation steps of the hollow mesoporous carbon nanospheres are the same as in example 1.
2、Sn/MoS2Preparation of the/C composite material: (1) 0.05g of potassium stannate trihydrate are weighed out and dissolved in 2mL of water and 4mL of ethanolAdding 15mg of urea and 25mg of hollow mesoporous carbon spheres into the mixed solvent under vigorous stirring, and vacuumizing for 10min under the system pressure of 20 kPa. Absorbing potassium stannate trihydrate into the hollow mesoporous carbon spheres. Heating the mixture in a tube furnace for 8 hours at 160 ℃ under argon atmosphere, and naturally cooling the mixture to room temperature after the reaction is finished to obtain tin dioxide/hollow mesoporous carbon spheres;
(2) 0.05g of ammonium molybdate tetrahydrate is dissolved in a mixed solvent of 2mL of water and 2mL of ethanol, 20mg of tin dioxide/hollow mesoporous carbon spheres are added under vigorous stirring, and then the mixture is vacuumized for 10min, and the system pressure is 20 kPa. Adsorbing the carbon powder into the tin dioxide/hollow mesoporous carbon spheres through capillary action, centrifuging and drying. 0.1g of sulfur powder was weighed, and the resulting composite material and sulfur powder were placed on both sides of a quartz boat, which was then heated to 400 ℃ in Ar. Keeping the mixture in a high-purity argon atmosphere for 3 hours to obtain tin disulfide/molybdenum disulfide/hollow mesoporous carbon spheres;
(3) calcining the prepared tin disulfide/molybdenum disulfide/hollow mesoporous carbon sphere material in a tubular furnace with 5% hydrogen content in argon-hydrogen mixed gas at 700 ℃ for 4h, and heating at the rate of 1 ℃/min to obtain Sn/MoS2a/C composite material. For Sn/MoS2TEM analysis at/C As shown in FIG. 7, at Sn/MoS2In the preparation of the/C composite material, because the dosage of the hollow mesoporous carbon spheres in the step (1) is increased, SnO filled into the hollow carbon spheres2Is reduced, resulting in subsequent MoS2The nanosheets and reduced Sn do not assemble into hollow spheres.
Sn/MoS2/C, preparation and electrochemical performance analysis of the composite material negative electrode: the preparation and analysis steps were the same as in example 1, and the results are shown in FIG. 8.
Comparative example 2
1. The preparation steps of the hollow mesoporous carbon nanospheres are the same as in example 1.
2、Sn/MoS2Preparation of the/C composite material: (1) 0.05g of potassium stannate trihydrate is weighed and dissolved in a mixed solvent of 2mL of water and 4mL of ethanol, 15mg of urea and 5mg of hollow mesoporous carbon spheres are added under vigorous stirring, and the mixture is vacuumized for 10min, and the system pressure is 20 kPa. Absorbing potassium stannate trihydrate into the hollow mesoporous carbon spheres. In a tube furnace under argon atmosphereHeating at 200 ℃ for 6h, and naturally cooling to room temperature after the reaction is finished to obtain stannic oxide/hollow mesoporous carbon spheres;
(2) 0.05g of ammonium molybdate tetrahydrate is dissolved in a mixed solvent of 2mL of water and 2mL of ethanol, 15mg of tin dioxide/hollow mesoporous carbon spheres are added under vigorous stirring, and then the mixture is vacuumized for 10min, and the system pressure is 20 kPa. Adsorbing the carbon powder into the tin dioxide/hollow mesoporous carbon spheres through capillary action, centrifuging and drying. 0.1g of sulfur powder was weighed, and the resulting composite material and sulfur powder were placed on both sides of a quartz boat, which was then heated to 600 ℃ in Ar. Keeping the mixture in a high-purity argon atmosphere for 2 hours to obtain tin disulfide/molybdenum disulfide/hollow mesoporous carbon spheres;
(3) calcining the prepared tin disulfide/molybdenum disulfide/hollow mesoporous carbon sphere material in a tubular furnace with 5% hydrogen content in argon-hydrogen mixed gas at 800 ℃ for 4h, and heating at the rate of 1 ℃/min to obtain Sn/MoS2a/C composite material.
Sn/MoS2/C, preparation and electrochemical performance analysis of the composite material negative electrode: the preparation and analysis steps were the same as in example 1, and the results are shown in FIG. 8.
As shown in FIG. 8, Sn/MoS prepared in example 22The @ C composite material has the best circulation stability, the dosage of each reaction material of the comparative example is not in the preferable proportioning range of the invention, and the prepared Sn/MoS2the/C composite material has slightly poor cycle stability compared with the examples.
Comparative example 3
The preparation steps of the hollow mesoporous carbon nanospheres are the same as in example 1.
Preparation of Sn @ C material: 0.05g of potassium stannate trihydrate is weighed and dissolved in a mixed solvent of 2mL of water and 2mL of ethanol, 25mg of urea and 10mg of hollow mesoporous carbon spheres are added under vigorous stirring, the vacuum pumping is carried out for 10min, and the system pressure is 20 kPa. Absorbing potassium stannate trihydrate into the hollow mesoporous carbon spheres. Heating the mixture for 6 hours at 120 ℃ in a tubular furnace under the argon atmosphere, naturally cooling the mixture to room temperature after the reaction is finished to obtain the tin dioxide @ hollow mesoporous carbon spheres, transferring the material to a hydrogen-argon mixed gas of 5% hydrogen and 600 ℃ tubular furnace, and calcining the material for 4 hours to obtain the Sn @ C material.
Preparation and electrochemical performance analysis of the Sn @ C material negative electrode: the preparation and analysis procedure were the same as in example 1, and the results are shown in FIG. 9.
Comparative example 4
The preparation steps of the hollow mesoporous carbon nanospheres are the same as in example 1.
MoS2@ C Material preparation: 0.05g of ammonium molybdate tetrahydrate is dissolved in a mixed solvent of 2mL of water and 2mL of ethanol, 25mg of hollow mesoporous carbon spheres are added under vigorous stirring, and then vacuum pumping is carried out for 10min, wherein the system pressure is 20 kPa. Adsorbing the carbon powder into the hollow mesoporous carbon spheres through capillary action, centrifuging and drying. 0.1g of sulfur powder was weighed, and the resulting composite material and sulfur powder were placed on both sides of a quartz boat, which was then heated to 600 ℃ in Ar. And keeping the solution in a high-purity argon atmosphere for 2 hours to obtain the molybdenum disulfide @ hollow mesoporous carbon spheres.
MoS2Preparation and electrochemical performance analysis of the @ C material negative electrode: the preparation and analysis procedure were the same as in example 1, and the results are shown in FIG. 9.
Comparative example 5
MoS2: commercial, chemical agents of the national drug group, ltd. MoS2Preparation and electrochemical performance analysis of the material cathode: the preparation and analysis procedure were the same as in example 1, and the results are shown in FIG. 9.
Comparative example 6
Sn: commercial tin powder 200 mesh, national drug group chemical reagents limited.
Preparation and electrochemical performance analysis of the Sn material negative electrode: the preparation and analysis procedure were the same as in example 1, and the results are shown in FIG. 9.
As shown in FIG. 9, Sn/MoS prepared in example 22The circulation stability of the @ C composite material is superior to that of comparative examples 3-6, and the Sn/MoS of the double-layer hollow sphere structure2Has higher specific capacity and stable cycle performance. This is due to the unique double-layer hollow sphere structure, and the Sn and MoS2The synergistic effect of (a).
The invention adopts hydrothermal and hydrogen calcination, the used method is simple, the instrument and equipment are simple, and the Sn/MoS with the double-layer hollow sphere structure can be obtained2@ C composite material. The first application of metallic tin to lithium ion is due to its high specific capacity characteristicsThe tin-based negative electrode material for a battery, but when it is applied to a lithium ion battery, it causes a large volume change and even pulverization of the material, thereby causing a problem of rapid capacity fade. Molybdenum disulfide as a material with a two-dimensional structure also has higher theoretical specific capacity, but good electrochemical performance is difficult to obtain due to the problems of poor conductivity and the like. Sn/MoS with double-layer hollow sphere structure2The performance of @ C combined material with these two kinds of materials to the structure with double-deck hollow ball further strengthens the two advantages, not only the effectual specific surface who increases the material promotes ion transport, and the space of double-deck hollow ball structure provides the buffering space for the inflation when material charge-discharge moreover. Has excellent electrochemical performance.
Claims (10)
1. Sn/MoS2The @ C composite material is characterized by being of a double-layer hollow sphere structure and composed of an internal hollow sphere and an outer spherical shell wrapping the internal hollow sphere, a gap exists between the internal hollow sphere and the outer spherical shell, and the internal hollow sphere is Sn/MoS2The outer layer of spherical shell is hollow mesoporous carbon spheres.
2. Sn/MoS according to claim 12The @ C composite material is characterized in that the internal hollow spheres are MoS bonded by Sn nanoparticles2The nano-sheets are assembled, the diameter of the spherical shell of the internal hollow sphere is 100-150 nm, and the thickness of the spherical shell is 10-15 nm.
3. Sn/MoS2The preparation method of the @ C composite material is characterized by comprising the following steps of:
(1) dissolving potassium stannate trihydrate and urea in a mixed solvent of water and ethanol, adding hollow mesoporous carbon spheres to obtain a mixed material, vacuumizing, calcining the mixed material in an argon atmosphere for reaction, and obtaining SnO after the reaction is finished2@C；
(2) Dissolving ammonium molybdate tetrahydrate in a mixed solvent of water and ethanol, and adding SnO in the step (1)2@ C to obtain a mixed material, then vacuumizing, adding sulfur powder into the mixed materialCalcining and reacting under argon atmosphere to obtain SnS after the reaction is finished2/MoS2@C；
(3) SnS in the step (2)2/MoS2Calcining at @ C in argon-hydrogen mixed atmosphere to obtain Sn/MoS2@ C composite material.
4. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (1), the mass ratio of the potassium stannate trihydrate, the urea and the hollow mesoporous carbon spheres is 1: 0.5-1: 0.1-0.2.
5. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (1) and/or the step (2), the vacuumizing time is 5-10min, and the system pressure is 20-40 kPa.
6. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (1), the calcination temperature is 100-200 ℃, the heating rate is 2-10 ℃/min, and the calcination time is 4-8 h.
7. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (2), ammonium molybdate tetrahydrate, sulfur powder and SnO2The mass ratio of @ C is 1: 1-2: 0.5-1.
8. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (2), the calcination temperature is 300-500 ℃, the heating rate is 1-5 ℃/min, and the calcination time is 1-4 h.
9. Sn/MoS according to claim 32The preparation method of the @ C composite material is characterized in that in the step (3), the calcination temperature is 600-800 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 1-4 h.
10. As claimed in any one of claims 1-2The Sn/MoS2The application of the @ C composite material as a lithium ion battery negative electrode material.
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