CN113097484A - Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof - Google Patents
Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-coated sandwich structure SnSe/r-GO @ C compound and a preparation method and application thereof2‑Moreover, oxygen-containing functional groups on graphene oxide can be reduced, the conductivity of graphene in the composite material is further improved, and the reducing agent can be effectively mixed with Sn2+Complexing, controllingThe size of the product, and the nano material is more effective for improving the electrochemical performance. The preparation method is simple and high in repeatability, the conductivity of the SnSe-based composite material is improved after the graphene oxide is added to carry out hydrothermal reaction, the structure stability of the composite material is further improved by coating a layer of pyrolytic carbon, and the composite material has good electrochemical performance when being used as a sodium ion electrode material.
Description
Technical Field
The invention relates to the technical field of sodium ion battery cathode materials, in particular to a carbon-coated sandwich-structured SnSe/r-GO @ C compound and a preparation method and application thereof.
Background
The sodium ion battery has an electrochemical energy storage principle similar to that of the lithium ion battery, and the sodium resource has rich reserves and low price, so the sodium ion battery is considered to be a secondary battery with great potential for realizing large-scale energy storage. However, Na+Is much larger than Li in diameter+The graphite negative electrode of commercial lithium ion battery shows poor Na+And (4) storing the performance. Therefore, the development of high-performance sodium storage negative electrode materials is of great importance for sodium ion batteries. Tin selenide is used as one of alloy cathode materials, and the sodium insertion capacity of the tin selenide is 780mAh g-1Has great development potential. In addition, SnSe is an important IV-VI semiconductor material, has an energy gap of about 0.9eV, and can be widely applied to infrared photoelectric devices, memory switches, thin film electrodes, solar cells and the like. At present, the performance of a sodium ion battery made of a tin selenide-based cathode material has great potential, but the charge-discharge structural stability of the sodium ion battery needs to be further improved. Many researchers have chosen to compound it with certain carbon materials to ameliorate the above problems, for example, xiaochean Ren et al have synthesized Sn-C bonded SnSe nanodiscs grown vertically on nitrogen doped carbon nanoribbons for use as negative electrode materials for high performance sodium ion batteries. Calculations show that the presence of N atoms in the NC matrix promotes the formation of Sn — C bonds. The SnSe has a lower interlayer Na ion diffusion barrier, and a smaller energy barrier from the discharge product Sn to the original SnSe/NC, which shows that the SnSe/NC has quick electrochemical kinetics and good reversibility.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a carbon-coated sandwich structure SnSe/r-GO @ C compound and a preparation method and application thereof.
In order to achieve the aim, the invention provides a preparation method of a carbon-coated sandwich structure SnSe/r-GO @ C compound, which comprises the following steps:
1) adding 30-90 mg of graphene oxide into 30-70 mL of ethylene glycol or glycerol, dispersing, adding 0.05696-5.696 g of inorganic tin salt, stirring, and then adding 0.02-0.2 g of surfactant until the surfactant is completely dissolved to obtain a solution A;
2) adding 0.01975 g-1.975 g of selenium powder into 3-10 ml of reducing solvent, and stirring until the selenium powder is completely dissolved to obtain a solution B; and dropwise adding the solution B into the solution A and stirring to form a mixed solution C, wherein the molar ratio of tin ions to selenium ions in the mixed solution C is 1: (1-4);
3) carrying out hydrothermal reaction on the mixed solution C at the temperature of 120-200 ℃, and cooling to obtain a black mixed solution D after the reaction is finished;
4) adding 10-30 g of graphene oxide into 10-20 ml of ethylene glycol or glycerol, dispersing to obtain a solution E, adding the solution E into the mixed solution D, and stirring to obtain a mixed solution F;
5) carrying out hydrothermal reaction on the mixed solution F at the temperature of 120-200 ℃, cooling after the reaction is finished to obtain a black mixed solution G, and carrying out suction filtration on the mixed solution G to obtain black powder;
6) and (2) carrying out freeze drying on the black powder obtained by suction filtration and collection to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, carrying out hydrothermal reaction on the mixture Y at 160-240 ℃, cooling to obtain black powder after the reaction is finished, and carrying out thermal treatment on the black powder to obtain the carbon-coated sandwich structure SnSe/r-GO @ C compound.
Further, the inorganic tin salt is SnCl2·2H2O。
Further, the surfactant is oleic acid.
Further, the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution.
Further, magnetic stirring is adopted for stirring, the stirring speed is 300-800 r/min, and the stirring time is 30-120 min.
Further, ultrasonic dispersion is adopted for dispersion, and the ultrasonic time is 90-180 min.
Furthermore, the hydrothermal reaction is carried out by adopting a hydrothermal kettle and placing the hydrothermal kettle in a hydrothermal reaction instrument, and the filling degree of the hydrothermal kettle is controlled to be 50-80%.
The invention also provides a carbon-coated sandwich structure SnSe/r-GO @ C compound which is prepared by the preparation method of the carbon-coated sandwich structure SnSe/r-GO @ C compound.
Furthermore, graphene oxide sheets in the composite are of a sandwich structure, SnSe nanoparticles grow on the graphene oxide sheets, pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nanoparticles is 5-8 nm.
The invention also provides an application of the carbon-coated sandwich structure SnSe/r-GO @ C compound, and the compound is mixed with a binder and a conductive agent to prepare the sodium-ion battery cathode material.
Compared with the prior art, the pure-phase carbon-coated sandwich SnSe/r-GO @ C composite is prepared by using ethylene glycol or glycerol as a solvent, inorganic tin salt as a tin source, ethylene diamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution as a reducing agent, oleic acid as a surfactant and a simple solvothermal method combined with a heat treatment method, wherein the size of SnSe nanoparticles is about 5-8 nm, and the ethylene diamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution and the like as the reducing agent can reduce selenium powder and provide Se powder2-Moreover, oxygen-containing functional groups on the graphene oxide can be reduced, the conductivity of the graphene in the composite material is further improved, and on the other hand, the reducing agent can be effectively added to Sn2+Complexing, controlling the size of the product, andthe nano material is more effective for improving the electrochemical performance. In addition, the preparation method adopted by the invention is simple and high in repeatability, the conductivity of the SnSe-based composite material is greatly improved after the graphene oxide is added for hydrothermal reaction, and the structure stability of the composite material can be effectively improved by coating a layer of pyrolytic carbon material on the basis of compounding with the graphene oxide, so that the composite material is expected to have better electrochemical performance when being used as a sodium ion electrode material.
The invention prepares a pure-phase SnSe/r-GO @ C compound with a carbon-coated sandwich structure, wherein r-GO is a uniformly-distributed sheet structure, SnSe quantum dots are uniformly distributed between an r-GO sheet and a sheet interlayer, SnSe nanoparticles are pure-phase SnSe particles with the size of about 5-8 nm, a layer of carbon material is coated outside the sandwich structure compound growing with tin selenide particles, and the compound electrode has good sodium ion storage performance. The invention has simple process, high repeatability, short preparation period and low reaction temperature, reduces energy consumption and production cost, and is suitable for large-scale production and preparation.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a composite prepared according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a composite prepared in example 1 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of the composite prepared in example 1 of the present invention.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a preparation method and application of a carbon-coated sandwich structure SnSe/r-GO @ C compound, which comprises the following steps:
step 1): adding 30-90 mg of graphene oxide GO into 30-70 mL of solvent of ethylene glycol or glycerol, performing ultrasonic dispersion, and adding 0.05696-5.696 g of SnCl2·2H2O, after being stirred evenly, 0.02g to 0.2g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 0.01975 g-1.975 g of selenium powder into 3-10 ml of ethylene diamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution, and stirring until the selenium powder is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring; wherein, the mol ratio of the tin ions to the selenium ions is 1: (1-4); the concentration of the graphene oxide in the solution A is 1-2 mg/mL-1；
Step 2): transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120-200 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 10-30G of graphene oxide into 10-20 ml of ethylene glycol or glycerol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, performing full reaction at 120-200 ℃, cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution G, performing suction filtration on the mixed solution G, and collecting black powder; and freeze-drying the powder obtained by suction filtration separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160-240 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to perform heat treatment to obtain a final product Z, namely the carbon-coated sandwich structure SnSe/r-GO @ C compound. In the preparation method, magnetic stirring is adopted for stirring, the stirring speed is 300-800 r/min, the stirring time is 30-120 min, the ultrasonic dispersion time is 90-180 min, and the filling degree of the hydrothermal kettle is controlled to be 50-80%.
The invention also provides a carbon-coated sandwich-structured SnSe/r-GO @ C compound prepared by the method, wherein fine SnSe nanoparticles are grown on the GO sheet, a sandwich structure is formed between the GO sheet and the GO sheet, the sandwich structure is represented as a sandwich-like structure, a layer of pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nanoparticles is about 5-8 nm.
The invention also provides application of the carbon-coated sandwich structure SnSe/r-GO @ C compound, when the compound is used as a sodium ion battery cathode material, the carbon-coated sandwich structure SnSe/r-GO @ C compound is mixed with a binder and a conductive agent according to the mass ratio of 8:1:1 to prepare a cathode sheet, the binder is carboxymethyl cellulose (CMC), and the conductive agent is super P.
The present invention will be described with reference to specific examples.
Example 1:
the preparation method comprises the following steps:
1) adding 30mg of graphene oxide GO into 30mL of ethylene glycol, adding 0.07595g of SnCl after ultrasonic dispersion2·2H2O, after being stirred uniformly, 0.02g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 0.0263g selenium powder into 3ml ethylenediamine water solution, stirring to dissolve completely to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 10g of graphene oxide into 10ml of ethylene glycol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, and stirring uniformly to obtain a mixed solution F; transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120 ℃, cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution G, carrying out suction filtration on the mixed solution G to obtain black powder, and carrying out freeze drying on the powder obtained by suction filtration separation to obtain a product X; and mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to perform heat treatment to obtain a final product Z.
The SnSe/r-GO @ C compound of the sample is analyzed by a Japanese science D/max2000 PCX-ray diffractometer, and the result is shown in figure 1, and the sample is found to be consistent with the SnSe structure with JCPDS number of 89-0232, which indicates that SnSe nano-particles are prepared. The sample is observed by a Field Emission Scanning Electron Microscope (FESEM), and as a result, referring to fig. 2, it can be seen that the prepared SnSe nanoparticles are uniformly dispersed on the surface of the sheet-shaped graphene oxide. The sample is observed by a Transmission Electron Microscope (TEM), and the result is shown in FIG. 3, wherein SnSe in the compound is nano-particles with the size of about 5-8 nm and uniformly grows on the surface of the flaky graphene oxide.
Example 2:
the preparation method comprises the following steps:
1) adding 45mg of graphene oxide GO into 50mL of glycerol, and adding 0.52785g of SnCl after ultrasonic dispersion2·2H2O, after being stirred evenly, 0.08g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 0.0789g selenium powder into 5ml triethanolamine aqueous solution, stirring until completely dissolving to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 140 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 10g of graphene oxide into 10ml of glycerol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 140 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution G, carrying out suction filtration and collection on the mixed solution G to obtain black powder, carrying out freeze drying on the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to obtain a final product Z through heat treatment.
Example 3:
the preparation method comprises the following steps:
1) adding 60mg of graphene oxide GO into 60mL of glycerol, and adding 1.0557g of SnCl after ultrasonic dispersion2·2H2O, after being stirred evenly, 0.12g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 0.2367g selenium powder into 6ml hydrazine hydrate, stirring until the selenium powder is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 20g of graphene oxide into 20ml of glycerol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution G, carrying out suction filtration and collection on the mixed solution G to obtain black powder, carrying out freeze drying on the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 200 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to obtain a final product Z through heat treatment.
Example 4:
the preparation method comprises the following steps:
1) adding 60mg of graphene oxide GO into 60mL of ethylene glycol, adding 3.1671g of SnCl after ultrasonic dispersion2·2H2O, after being stirred evenly, 0.15g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; 0.7101g of selenium powder is added into 5ml of sodium borohydride aqueous solution, and the solution B is obtained after stirring and complete dissolution; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 20g of graphene oxide into 20ml of ethylene glycol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution G, carrying out suction filtration and collection on the mixed solution G to obtain black powder, carrying out freeze drying on the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 220 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to obtain a final product Z through heat treatment.
Example 5:
the preparation method comprises the following steps:
1) adding 90mg of graphene oxide GO into 60mL of ethylene glycol, adding 5.696g of SnCl after ultrasonic dispersion2·2H2O, after being stirred evenly, 0.2g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 1.975g of selenium powder into 5ml of hydrazine hydrate, and stirring until the selenium powder is completely dissolved to obtain a solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 20g of graphene oxide into 20ml of ethylene glycol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution G, carrying out suction filtration and collection on the mixed solution G to obtain black powder, carrying out freeze drying on the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 240 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and placing the black powder in a tubular furnace to obtain a final product Z through heat treatment.
Example 6:
the preparation method comprises the following steps:
1) adding 30mg of graphene oxide GO into 30mL of glycerol, and adding 0.05696g of SnCl after ultrasonic dispersion2·2H2O, after being stirred uniformly, 0.02g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; adding 0.01975g of selenium powder into 3ml of triethanolamine aqueous solution, and stirring until the selenium powder is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 10G of graphene oxide into 10ml of glycerol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, performing full reaction at 120 ℃, cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution G, and performing suction filtration and collection on the mixed solution G to obtain black powder; freeze-drying the powder obtained by suction filtration separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, cooling to room temperature along with a furnace after the reaction is finished to obtain black powder, placing the black powder into a tubular furnace, and carrying out heat treatment to obtain a final product Z.
Example 7:
the preparation method comprises the following steps:
1) adding 90mg of graphene oxide GO into 70mL of ethylene glycol, adding 5.696g of SnCl after ultrasonic dispersion2·2H2O, after being stirred uniformly, 0.2g of oleic acid is added until the oleic acid is completely dissolved to form a solution A; 1.975g of selenium powder is added into 10ml of ethylenediamine aqueous solution,stirring until the solution is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A to form a mixed solution C, and uniformly stirring;
2) transferring the mixed solution C into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 200 ℃, and cooling to room temperature along with the furnace after the reaction is finished to obtain a black mixed solution D; adding 30G of graphene oxide into 20ml of ethylene glycol, performing ultrasonic dispersion uniformly to obtain a solution E, adding the solution E into the solution D, stirring uniformly to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, performing full reaction at 200 ℃, cooling the mixed solution F to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution G, performing suction filtration on the mixed solution G, and collecting black powder; freeze-drying the powder obtained by suction filtration separation to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, then placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 240 ℃, cooling to room temperature along with a furnace after the reaction is finished to obtain black powder, placing the black powder into a tubular furnace, and carrying out heat treatment to obtain a final product Z.
The carbon-coated sandwich structure SnSe/r-GO @ C compound is prepared by using ethylene glycol or glycerol as a solvent and adopting a simple solvothermal method, wherein SnSe nanoparticles are pure-phase nanoparticles with the size of about 5-8 nm and are uniformly dispersed among the flaky graphene oxide interlayers. The preparation method is simple and short in period, the graphene oxide and the pyrolytic carbon are used as carbon matrixes, the conductivity of the SnSe is improved, the structural stability of the composite material is improved, the composite material serving as a negative electrode material of the sodium ion battery has good electrochemical performance, and researches show that the pseudo-capacitance effect exists in the electrode sodium storage process of the SnSe/r-GO @ C composite material, so that the composite material has great research value. The composite material is used as a photocatalytic material and an electrode material, and has good photocatalytic and electrochemical properties.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a carbon-coated sandwich structure SnSe/r-GO @ C compound is characterized by comprising the following steps:
1) adding 30-90 mg of graphene oxide into 30-70 mL of ethylene glycol or glycerol, dispersing, adding 0.05696-5.696 g of inorganic tin salt, stirring, and then adding 0.02-0.2 g of surfactant until the surfactant is completely dissolved to obtain a solution A;
2) adding 0.01975 g-1.975 g of selenium powder into 3-10 ml of reducing solvent, and stirring until the selenium powder is completely dissolved to obtain a solution B; and dropwise adding the solution B into the solution A and stirring to form a mixed solution C, wherein the molar ratio of tin ions to selenium ions in the mixed solution C is 1: (1-4);
3) carrying out hydrothermal reaction on the mixed solution C at the temperature of 120-200 ℃, and cooling to obtain a black mixed solution D after the reaction is finished;
4) adding 10-30 g of graphene oxide into 10-20 ml of ethylene glycol or glycerol, dispersing to obtain a solution E, adding the solution E into the mixed solution D, and stirring to obtain a mixed solution F;
5) carrying out hydrothermal reaction on the mixed solution F at the temperature of 120-200 ℃, cooling after the reaction is finished to obtain a black mixed solution G, and carrying out suction filtration on the mixed solution G to obtain black powder;
6) and (2) carrying out freeze drying on the black powder obtained by suction filtration and collection to obtain a product X, mixing and grinding the product X and an organic matter 2-methylimidazole solid phase to obtain a mixture Y, carrying out hydrothermal reaction on the mixture Y at 160-240 ℃, cooling to obtain black powder after the reaction is finished, and carrying out thermal treatment on the black powder to obtain the carbon-coated sandwich structure SnSe/r-GO @ C compound.
2. The SnSe of claim 1, wherein the SnSe is a carbon-coated sandwich-like structureThe preparation method of the/r-GO @ C compound is characterized in that the inorganic tin salt is SnCl2·2H2O。
3. The method for preparing the SnSe/r-GO @ C composite with the carbon-coated sandwich structure according to claim 1, wherein the surfactant is oleic acid.
4. The method for preparing the SnSe/r-GO @ C composite with the carbon-coated sandwich structure according to claim 1, wherein the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or aqueous sodium borohydride solution.
5. The preparation method of the SnSe/r-GO @ C compound with the carbon-coated sandwich structure as claimed in claim 1, wherein the stirring is performed by magnetic stirring, the stirring speed is 300-800 r/min, and the stirring time is 30-120 min.
6. The preparation method of the SnSe/r-GO @ C composite with the carbon-coated sandwich structure according to claim 1, wherein the dispersion is ultrasonic dispersion for 90-180 min.
7. The preparation method of the SnSe/r-GO @ C compound with the carbon-coated sandwich structure according to claim 1, wherein the hydrothermal reaction is carried out by using a hydrothermal kettle and placing the hydrothermal kettle in a hydrothermal reactor, and the filling degree of the hydrothermal kettle is controlled to be 50-80%.
8. A carbon-coated sandwich-structured SnSe/r-GO @ C compound, which is characterized by being prepared by the preparation method of the carbon-coated sandwich-structured SnSe/r-GO @ C compound in any one of claims 1 to 7.
9. The SnSe/r-GO @ C composite with the carbon-coated sandwich structure of claim 8, wherein graphene oxide sheets in the composite are of a sandwich structure, SnSe nanoparticles grow on the graphene oxide sheets, pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nanoparticles is 5-8 nm.
10. The application of the SnSe/r-GO @ C composite with the carbon-coated sandwich structure as set forth in claim 8 or 9, wherein the composite is mixed with a binder and a conductive agent to prepare a negative electrode material of a sodium-ion battery.
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