CN113097484B - Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof - Google Patents

Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof Download PDF

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CN113097484B
CN113097484B CN202110353501.8A CN202110353501A CN113097484B CN 113097484 B CN113097484 B CN 113097484B CN 202110353501 A CN202110353501 A CN 202110353501A CN 113097484 B CN113097484 B CN 113097484B
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黄剑锋
胡炎杰
王芳敏
李嘉胤
曹丽云
王佳乐
刘旭华
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a SnSe/r-GO@C compound with a carbon-coated sandwich structure, a preparation method and application thereof, wherein ethylene glycol or glycerin is used as a solvent, inorganic tin salt is used as a tin source, a reducing agent and a surfactant are used, the SnSe/r-GO compound with the carbon-coated sandwich structure is prepared by adopting a simple solvothermal method, and the reducing agent not only can reduce selenium powder, but also can provide Se 2‑ The oxygen-containing functional groups on the graphene oxide can be reduced, the conductivity of the graphene in the composite material is further improved, and the addition of the reducing agent can be effectively matched with Sn 2+ Complexing, controlling the size of the product, while nanocrystallized materials are more effective for enhancing electrochemical performance. The preparation method disclosed by the invention is simple, the repeatability is high, the conductivity of the SnSe-based composite material is improved after the graphene oxide is added for hydrothermal reaction, a layer of pyrolytic carbon is coated, the structural stability of the composite material is further improved, and the composite material has better electrochemical performance when being used as a sodium ion electrode material.

Description

Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a carbon-coated sandwich-like structure SnSe/r-GO@C compound and a preparation method and application thereof.
Background
Sodium ion batteries have electrochemical energy storage similar to lithium ion batteriesThe principle is that sodium resources are abundant in reserve and low in price, and the sodium resources are considered as secondary batteries with great potential for realizing large-scale energy storage. However Na is + Is far larger than Li + Commercial lithium ion battery graphite negative electrode shows poor Na + Storage performance. Therefore, the development of high-performance sodium storage anode materials is important for sodium ion batteries. Tin selenide serving as one of alloy anode materials has sodium intercalation capacity of 780mAh g -1 Has 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, storage switches, thin film electrodes, solar cells and the like. At present, the performance of the sodium ion battery of the tin selenide-based anode material has great potential, but the stability of the charge-discharge structure of the sodium ion battery still needs to be further improved. Many researchers have chosen to combine it with certain carbon materials to ameliorate the above problems, for example, the synthesis of Sn-C bond linked SnSe nanodiscs by Xiaochuan Ren et al vertically grown on nitrogen doped carbon nanoribbons for use as negative electrode materials in high performance sodium ion batteries. The presence of N atoms in the NC matrix has been shown by calculation to promote the formation of Sn-C bonds. SnSe has a low interlayer Na ion diffusion barrier, and has a small energy barrier from a discharge product Sn to original SnSe/NC, so that the SnSe/NC has rapid electrochemical dynamics and good reversibility.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the SnSe/r-GO@C compound with the carbon-coated sandwich structure, the preparation method and the application thereof, wherein nano-granular SnSe uniformly grows between flaky graphene oxide interlayers, and a layer of carbon material is coated outside the sandwich structure compound with the tin selenide particles, so that the sandwich structure compound has a stable structure and has better electrochemical performance as a sodium ion electrode material.
In order to achieve the above purpose, the invention provides a preparation method of a carbon-coated sandwich-like 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 glycerin, dispersing, adding 0.05696-5.696 g of inorganic tin salt, stirring, and adding 0.02-0.2 g of surfactant until the solution A is completely dissolved;
2) 0.01975 g-1.975 g selenium powder is added into 3-10 ml reducing solvent, and stirred until the selenium powder is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A and stirring to form a mixed solution C, wherein the mole 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 after the reaction is finished to obtain black mixed solution D;
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 120-200 ℃, cooling after the reaction is finished to obtain black mixed solution G, and carrying out suction filtration and collection on the mixed solution G to obtain black powder;
6) And freeze-drying the black powder obtained by suction filtration to obtain a product X, mixing and grinding the product X and an organic 2-methylimidazole solid phase to obtain a mixture Y, carrying out hydrothermal reaction on the mixture Y at 160-240 ℃, cooling after the reaction is finished to obtain the black powder, and carrying out heat treatment on the black powder to obtain the SnSe/r-GO@C compound with the carbon-coated sandwich structure.
Further, the inorganic tin salt is SnCl 2 ·2H 2 O。
Further, the surfactant is oleic acid.
Further, the reducing solvent is ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution.
Further, the stirring adopts magnetic stirring, the stirring speed is 300-800 r/min, and the stirring time is 30-120 min.
Further, the dispersion adopts ultrasonic dispersion, and the ultrasonic time is 90-180 min.
Further, the hydrothermal reaction is carried out by adopting 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%.
The invention also provides the SnSe/r-GO@C compound with the carbon-coated sandwich structure, which is prepared by adopting the preparation method of the SnSe/r-GO@C compound with the carbon-coated sandwich structure.
Further, graphene oxide sheets in the compound are of a sandwich structure, snSe nano particles grow on the graphene oxide sheets, pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nano particles is 5-8 nm.
The invention also provides application of the SnSe/r-GO@C compound with the carbon-coated sandwich structure, and the compound is mixed with a binder and a conductive agent to prepare the negative electrode material of the sodium ion battery.
Compared with the prior art, the invention uses ethylene glycol or glycerin as a solvent, inorganic tin salt as a tin source, ethylenediamine, 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 to prepare the SnSe/r-GO@C composite with a pure-phase carbon-coated sandwich structure, wherein the size of SnSe nano particles is about 5-8 nm, and the ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride aqueous solution and the like are used as the reducing agent to reduce selenium powder and provide Se 2- In addition, the oxygen-containing functional group on the graphene oxide can be reduced, so that the conductivity of the graphene in the composite material is further improved, and on the other hand, the reducing agent can be effectively added with Sn 2+ Complexing, controlling the size of the product, while nanocrystallized materials are more effective for enhancing electrochemical performance. In addition, the preparation method adopted by the invention is simple, the repeatability is high, the conductivity of the SnSe-based composite material is greatly improved after the graphene oxide is added for hydrothermal reaction, and a layer of pyrolytic carbon material is coated on the basis of compounding the SnSe-based composite material with the graphene oxide, so that the structural stability of the composite can be effectively improved, and the composite material is expected to have better electrochemical performance as a sodium ion electrode material.
The invention prepares a pure-phase SnSe/r-GO@C compound with a sandwich structure, r-GO is a uniformly distributed sheet structure, snSe quantum dots are uniformly distributed between r-GO sheets and sheet interlayers, snSe nano particles are pure-phase SnSe particles, the size of the particles is about 5-8 nm, a layer of carbon material is coated outside the sandwich structure compound with the tin selenide particles, the structural stability of the composite electrode is improved, the composite electrode has better sodium ion storage performance, and researches find that the composite electrode has pseudo-capacitance effect in the sodium storage process and has great research value. The invention has simple process, high repeatability, short preparation period, low reaction temperature, reduced 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 in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the compound prepared in example 1 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of the compound prepared in example 1 of the present invention.
Detailed Description
The present invention will be further illustrated by the following description, taken in conjunction with the accompanying drawings and specific embodiments, and it will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The invention provides a preparation method and application of a carbon-coated sandwich-like structure SnSe/r-GO@C compound, comprising the following steps of:
step 1): 30-90 mg of graphene oxide GO is added into 30-70 mL of ethylene glycol or glycerin solvent, and 0.05696-5.696 g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being uniformly stirred, adding 0.02 g-0.2 g of oleic acid until the oleic acid is completely dissolved to form solution A; 0.01975 g-1.975 g selenium powder is added into 3-10 ml ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride water solution, and stirred 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; wherein, the mol ratio of tin ions to 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, uniformly dispersing by ultrasonic to obtain a solution E, adding the solution E into a solution D, uniformly stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120-200 ℃, cooling to room temperature along with a furnace 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; freeze-drying the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160-240 ℃, cooling the mixture along with a furnace to room temperature after the reaction is finished to obtain black powder, and placing the black powder into a tubular furnace to obtain a final product Z, namely the carbon-coated sandwich-like SnSe/r-GO@C compound. In the preparation method, magnetic stirring is adopted, 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 the SnSe/r-GO@C compound with the carbon-coated sandwich-like structure, which is prepared by the method, wherein fine SnSe nano particles grow on GO sheets, the sandwich structure is formed between the GO sheets, the sandwich structure is represented by a sandwich-like structure, a layer of pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nano particles is about 5-8 nm.
The invention also provides application of the SnSe/r-GO@C composite of the carbon-coated sandwich structure, when the composite is used as a negative electrode material of a sodium ion battery, the SnSe/r-GO@C composite of the carbon-coated sandwich structure, a binder and a conductive agent are mixed according to a mass ratio of 8:1:1 to prepare a negative electrode plate, wherein the binder is carboxymethyl cellulose CMC, and the conductive agent is super P.
The invention will now be described with reference to specific examples.
Example 1:
the preparation method comprises the following steps:
1) 30mg of graphene oxide GO is added into 30mL of ethylene glycol, and 0.07595g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being stirred uniformly, adding 0.02g of oleic acid until the oleic acid is completely dissolved to form 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120 ℃, and cooling to room temperature along with a 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 uniformly stirring 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 and collection on the mixed solution G to obtain black powder, and freeze-drying the powder obtained by suction filtration and separation to obtain a product X; and (3) mixing and grinding the product X and the organic 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, cooling the mixture along with a furnace to room temperature 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.
The sample SnSe/r-GO@C complex is analyzed by adopting a Japanese physics 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, thereby indicating that the SnSe nano particles are prepared. The sample was observed with a Field Emission Scanning Electron Microscope (FESEM), and as a result, referring to fig. 2, it can be seen that the prepared SnSe nanoparticles were uniformly dispersed on the surface of the flaky graphene oxide. When the sample was observed by a Transmission Electron Microscope (TEM), it was seen from fig. 3 that SnSe in the composite was nanoparticles having a size of about 5 to 8nm, and uniformly grown on the surface of the flaky graphene oxide.
Example 2:
the preparation method comprises the following steps:
1) 45mg of graphene oxide GO is added into 50mL of glycerin, and 0.52785g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being stirred uniformly, adding 0.08g of oleic acid until the oleic acid is completely dissolved to form solution A; 0.0789g of selenium powder is added into 5ml of triethanolamine water solution, and the mixture is stirred 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 140 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 10G of graphene oxide into 10ml of glycerin, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 140 ℃, cooling to room temperature along with a 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 suction filtration and separation on the obtained powder, freeze-drying to obtain a product X, carrying out solid phase mixing and grinding on the product X and organic 2-methylimidazole to obtain a mixture Y, transferring the mixture Y into the hydrothermal kettle, placing the hydrothermal kettle into the hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain the black powder, and carrying out heat treatment on the black powder in a tubular furnace to obtain a final product Z.
Example 3:
the preparation method comprises the following steps:
1) 60mg of graphene oxide GO is added into 60mL of glycerin, and 1.0557g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being uniformly stirred, adding 0.12g of oleic acid until the oleic acid is completely dissolved to form solution A; 0.2367g of selenium powder is added into 6ml of hydrazine hydrate and stirred 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 20G of graphene oxide into 20ml of glycerin, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, 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 a black mixed solution G, carrying out suction filtration and collection on the mixed solution G to obtain black powder, carrying out suction filtration and separation on the obtained powder, freeze-drying to obtain a product X, carrying out solid phase mixing and grinding on the product X and organic 2-methylimidazole to obtain a mixture Y, transferring the mixture Y into the hydrothermal kettle, placing the hydrothermal kettle into the hydrothermal reactor, fully reacting at 200 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain the black powder, and carrying out heat treatment on the black powder in a tubular furnace to obtain a final product Z.
Example 4:
the preparation method comprises the following steps:
1) 60mg of graphene oxide GO is added into 60mL of ethylene glycol, and 3.1671g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being uniformly stirred, adding 0.15g of oleic acid until the oleic acid is completely dissolved to form solution A; 0.7101g of selenium powder is added into 5ml of sodium borohydride aqueous solution, and stirred 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 20G of graphene oxide into 20ml of ethylene glycol, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with a 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 suction filtration and separation on the obtained powder, freeze-drying to obtain a product X, carrying out solid phase mixing and grinding on the product X and organic 2-methylimidazole to obtain a mixture Y, transferring the mixture Y into the hydrothermal kettle, placing the hydrothermal kettle into the hydrothermal reactor, fully reacting at 220 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and carrying out heat treatment on the black powder in a tubular furnace to obtain a final product Z.
Example 5:
the preparation method comprises the following steps:
1) 90mg of graphene oxide GO is added into 60mL of ethylene glycol, and 5.696g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being uniformly stirred, adding 0.2g of oleic acid until the oleic acid is completely dissolved to form 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 20G of graphene oxide into 20ml of ethylene glycol, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 180 ℃, cooling to room temperature along with a 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 suction filtration and separation on the obtained powder, freeze-drying to obtain a product X, carrying out solid phase mixing and grinding on the product X and organic 2-methylimidazole to obtain a mixture Y, transferring the mixture Y into the hydrothermal kettle, placing the hydrothermal kettle into the hydrothermal reactor, fully reacting at 240 ℃, cooling to room temperature along with the furnace after the reaction is finished to obtain black powder, and carrying out heat treatment on the black powder in a tubular furnace to obtain a final product Z.
Example 6:
the preparation method comprises the following steps:
1) 30mg of graphene oxide GO is added into 30mL of glycerin, and 0.05696g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being stirred uniformly, adding 0.02g of oleic acid until the oleic acid is completely dissolved to form solution A; 0.01975g of selenium powder is added into 3ml of triethanolamine water solution, and the mixture is stirred until the selenium powder is completely dissolved to obtain solution B; then adding the solution B into the solution A dropwise to form a mixtureSolution C, and stirring uniformly;
2) Transferring the mixed solution C into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 120 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 10G of graphene oxide into 10ml of glycerin, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, 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, and carrying out suction filtration on the mixed solution G to obtain black powder; and freeze-drying the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 160 ℃, cooling the mixture along with a furnace to room temperature 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 7:
the preparation method comprises the following steps:
1) 90mg of graphene oxide GO is added into 70mL of ethylene glycol, and 5.696g of SnCl is added after ultrasonic dispersion 2 ·2H 2 O, after being uniformly stirred, adding 0.2g of oleic acid until the oleic acid is completely dissolved to form solution A; adding 1.975g of selenium powder into 10ml of ethylenediamine water solution, 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, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 200 ℃, and cooling to room temperature along with a furnace after the reaction is finished to obtain a black mixed solution D; adding 30G of graphene oxide into 20ml of ethylene glycol, carrying out ultrasonic dispersion to obtain a solution E, adding the solution E into a solution D, stirring to obtain a mixed solution F, transferring the mixed solution F into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 200 ℃, cooling to room temperature along with a furnace 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; and freeze-drying the powder obtained by suction filtration and separation to obtain a product X, mixing and grinding the product X and an organic 2-methylimidazole solid phase to obtain a mixture Y, transferring the mixture Y into a hydrothermal kettle, placing the hydrothermal kettle into a hydrothermal reactor, fully reacting at 240 ℃, cooling the mixture along with a furnace to room temperature 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.
According to the invention, ethylene glycol or glycerol is used as a solvent, and a simple solvothermal method is adopted to prepare the SnSe/r-GO@C compound with a carbon-coated sandwich structure, wherein SnSe nano particles are pure-phase nano particles with the size of about 5-8 nm and are uniformly dispersed among lamellar graphene oxide interlayers. The preparation method is simple and short in period, graphene oxide and pyrolytic carbon are used as carbon matrixes, so that the conductivity of SnSe is improved, the structural stability of a composite material is improved, the composite material is used as a negative electrode material of a sodium ion battery, the electrochemical performance is good, and the research discovers that a pseudocapacitance effect exists in the sodium storage process of the SnSe/r-GO@C composite electrode, so that the composite material has a high research value. The composite material is used as a photocatalysis material and an electrode material, and has good photocatalysis and electrochemical performances.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the technical solutions according to the embodiments of the present invention.

Claims (10)

1. The preparation method of the SnSe/r-GO@C compound with the carbon-coated sandwich structure is characterized by comprising the following steps of:
1) Adding 30-90 mg of graphene oxide into 30-70 mL of ethylene glycol or glycerin, dispersing, adding 0.05696-5.696 g of inorganic tin salt, stirring, and adding 0.02-0.2 g of surfactant until the solution A is completely dissolved;
2) 0.01975 g-1.975 g selenium powder is added into 3-10 ml reducing solvent, and stirred until the selenium powder is completely dissolved to obtain solution B; then dropwise adding the solution B into the solution A and stirring to form a mixed solution C, wherein the mole 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 after the reaction is finished to obtain black mixed solution D;
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 120-200 ℃, cooling after the reaction is finished to obtain black mixed solution G, and carrying out suction filtration and collection on the mixed solution G to obtain black powder;
6) And freeze-drying the black powder obtained by suction filtration to obtain a product X, mixing and grinding the product X and an organic 2-methylimidazole solid phase to obtain a mixture Y, carrying out hydrothermal reaction on the mixture Y at 160-240 ℃, cooling after the reaction is finished to obtain the black powder, and carrying out heat treatment on the black powder to obtain the SnSe/r-GO@C compound with the carbon-coated sandwich structure.
2. The method for preparing the carbon-coated sandwich-like structure SnSe/r-GO@C compound according to claim 1, wherein the inorganic tin salt is SnCl 2 ·2H 2 O。
3. The method for preparing the SnSe/r-GO@C compound with carbon-coated sandwich structure according to claim 1, wherein the surfactant is oleic acid.
4. The method for preparing the SnSe/r-GO@C compound with carbon-coated sandwich structure according to claim 1, wherein the reducing solvent is an aqueous solution of ethylenediamine, triethanolamine, hydrazine hydrate or sodium borohydride.
5. The preparation method of the SnSe/r-GO@C compound with the carbon-coated sandwich structure according to claim 1, wherein magnetic stirring is adopted, 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 compound with the carbon-coated sandwich structure according to claim 1, wherein the dispersion is carried out by adopting ultrasonic dispersion, and the ultrasonic time is 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 performed by adopting 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. The carbon-coated sandwich-like structure SnSe/r-GO@C compound is characterized by being prepared by adopting the preparation method of the carbon-coated sandwich-like structure SnSe/r-GO@C compound as claimed in any one of claims 1 to 7.
9. The carbon-coated sandwich-like structure SnSe/r-GO@C compound according to claim 8, wherein graphene oxide sheets in the compound are of a sandwich structure, snSe nano particles grow on the graphene oxide sheets, pyrolytic carbon is coated outside the sandwich structure, and the size of the SnSe nano particles is 5-8 nm.
10. The application of the carbon-coated sandwich-like structure SnSe/r-GO@C compound according to claim 8 or 9, wherein the compound is mixed with a binder and a conductive agent to prepare a sodium ion battery anode material.
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CN114843464A (en) * 2022-04-21 2022-08-02 陕西科技大学 Three-dimensional cross-linked structure SnSe/3D r-GO composite material and preparation method and application thereof
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110212176A (en) * 2019-05-16 2019-09-06 南京工业大学 A kind of graphene/molybdenum disulfide nano ball/carbon black composite material preparation method
CN110492068A (en) * 2019-08-05 2019-11-22 中南大学 Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof
CN111180707A (en) * 2020-01-14 2020-05-19 中南大学 Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103887488B (en) * 2014-04-04 2015-12-02 哈尔滨工业大学 Lithium ion battery peach kernel shape SnO 2the preparation method of-Graphene-carbon composite
CN106328952A (en) * 2015-06-18 2017-01-11 中国石油化工股份有限公司 Lithium electrode material, and preparation method and application thereof
CN105964238A (en) * 2016-07-26 2016-09-28 宁波大学 Porous carbon coated ZnO nanometer composite material and preparing method thereof
CN107123794B (en) * 2017-05-08 2019-11-15 陕西科技大学 A kind of preparation method of carbon coating manganese monoxide/N doping redox graphene lithium ion battery negative material
CN107017395B (en) * 2017-05-22 2020-04-21 中南大学 Carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with sandwich structure and preparation method and application thereof
CN107893218B (en) * 2017-10-27 2020-01-10 苏州大学 Titanium dioxide/sulfonated graphene oxide/silver nanoparticle composite membrane and preparation method and application thereof
CN107887592B (en) * 2017-11-17 2020-09-01 武汉理工大学 Carbon-coated ZnO nanowire and preparation method and application thereof
CN109052367B (en) * 2018-09-30 2020-02-14 华中科技大学 Preparation method of pyridine nitrogen-enriched ultrathin carbon nanosheet material and metal composite material thereof
CN109585831B (en) * 2018-12-04 2022-04-01 浙江理工大学 Composite material with sandwich structure and preparation method and application thereof
CN109742353B (en) * 2018-12-29 2021-05-25 陕西科技大学 SnSe quantum dot/r-GO compound and preparation method and application thereof
CN111825119A (en) * 2019-04-23 2020-10-27 赵彦霖 Preparation method of zinc ion battery positive electrode material
CN112490430A (en) * 2020-12-07 2021-03-12 江苏师范大学 Preparation method of high-performance negative electrode material for lithium/sodium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110212176A (en) * 2019-05-16 2019-09-06 南京工业大学 A kind of graphene/molybdenum disulfide nano ball/carbon black composite material preparation method
CN110492068A (en) * 2019-08-05 2019-11-22 中南大学 Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof
CN111180707A (en) * 2020-01-14 2020-05-19 中南大学 Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李婷 ; 龙志辉 ; 张道洪 ; .Fe_2O_3/rGO纳米复合物的制备及其储锂和储钠性能.物理化学学报.2016,(第02期),全文. *
钱翔英 ; .三明治结构G@SnO_2 @C复合材料的合成、表征及其钠离子电池负极性能研究.电子显微学报.2019,(第02期),全文. *

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