CN106784678A - A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound - Google Patents

A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound Download PDF

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CN106784678A
CN106784678A CN201611180010.3A CN201611180010A CN106784678A CN 106784678 A CN106784678 A CN 106784678A CN 201611180010 A CN201611180010 A CN 201611180010A CN 106784678 A CN106784678 A CN 106784678A
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graphene oxide
snse
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CN106784678B (en
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黄剑锋
程娅伊
李嘉胤
曹丽云
许占位
罗艺佳
周磊
罗晓敏
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Shaanxi University of Science and Technology
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Abstract

The present invention provides a kind of solvent-thermal method and prepares flower-shaped SnSe2The method of graphene oxide compound.The preparation technology is as follows：Graphene oxide is first disperseed standby in ethanol, a certain amount of selenium powder then is added into dissolving in hydrazine hydrate forms claret solution, then by a certain amount of SnCl2·2H2O dissolves in ethanol and oleyl amine is added dropwise and forms mixed solution, during the mixed liquor and above-mentioned claret solution finally dropped into the mixed solution of Graphene respectively, it is transferred to after stirring in water heating kettle and 6~24h is incubated at 150~180 DEG C, is collected precipitation and obtain SnSe2With the compound of Graphene.The preparation process is simple that the present invention is used, the appearance and size of product is controllable, and repeatability is high, and greatly improves SnSe2The electric conductivity of sill, with certain scientific meaning.

Description

A kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound
【Technical field】
The present invention relates to SnSe2The preparation method of-graphene oxide compound, and in particular to a kind of solvent-thermal method prepares flower Shape SnSe2The method of-graphene oxide compound.
【Background technology】
Stannic selenide is a kind of important semi-conducting material, and its rich content, environment-friendly, stable chemical nature, because
And have important application at many aspects, especially resistance-variable storing device, infrared electro device, solar cell and The aspects such as lithium ion battery.In recent years, the focus as research is even more as the negative material of lithium ion/sodium-ion battery, but There is document report to point out, although stannic selenide as negative material with theoretical capacity higher, itself relatively low electronics/from Electron conductivity, and volumetric expansion strong influence larger during embedding lithium/sodium chemical property so that charge and discharge electric capacity Amount rapid decay.
In order to improve the electronic conductivity of stannic selenide, alleviate volumetric expansion, many researchers are answered stannic selenide and carbon Close, on the one hand improve the electric conductivity of composite, another aspect carbon can to a certain extent be alleviated as matrix and discharge The volumetric expansion problem of journey.Zhian Zhang etc. using tin and selenium powder as raw material, conductive black as carbon source, using ball milling Method is prepared for stannic selenide with the composite of carbon as lithium/sodium-ion battery negative pole, and composite wood is improved to a certain extent Electric conductivity (Zhian Zhang, Xingxing Zhao, Jie Li, the SnSe/carbon nanocomposite of material synthesized by high energy ball milling as an anode material for sodium-ion and lithium-ion batteries,Electrochimica Acta,2015,176 1296–1301)；Long Zhang To make stannic selenide nanoparticle growth in the inside of carbon fiber Deng the method for depositing is powered up by ball milling, substantially increase composite wood The structural stability of material, alleviates volumetric expansion (Long Zhanga, Lei Lua, the Dechao Zhang in charge and discharge process Et.al, Dual-buffered SnSe@CNFs as negative electrode with outstanding lithium Storage performance, Electrochimica Acta, 2016,209,423-429)；Zhang Zhian etc. using pink salt and Selenite is raw material, and the nanometer tin selenide homoepitaxial of sheet-like morphology is prepared in oxidation using hydro-thermal method and subsequent calcination The anode material of graphenic surface, excellent chemical property (Zhang Zhi is shown as anode material of lithium-ion battery Peace, Zhao Xingxing opens a kind of beautiful etc., stannic selenide/graphene oxide anode material and its preparation side for sodium-ion battery Method, China Patent No.：201510046305.0).
As can be seen here, the means of the really a kind of effective raising stannic selenide chemical property being combined with carbon.But The preparation method reported at present, the relatively complicated complexity of process, even with Large expensive equipment.Therefore, prepared by exploitation one kind Method is simple, and it is particularly important to be capable of the method for Effective Regulation product structure.
【The content of the invention】
Flower-shaped SnSe is prepared it is an object of the invention to provide a kind of solvent-thermal method2The method of-graphene oxide compound, Prepared SnSe2- graphene oxide compound is the SnSe of flower-like structure2The uniform surface for being grown in Graphene, its structure Stability, it is contemplated that there is preferable chemical property as lithium/sodium ion electrode material.
To reach above-mentioned purpose, present invention employs following technical scheme：
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound, comprises the following steps：
1) add graphene oxide into ethanol, ultrasonic disperse obtains solution A；Take selenium powder to be added in hydrazine hydrate, stir Mix and uniformly obtain claret solution B；Take inorganic tin salts and be added to ethanol until completely dissolved, be added dropwise over oleyl amine, form solution C；Then solution C and solution B be added dropwise to respectively form mixed solution in solution A, and stirred；In solution selenium powder with The mol ratio of inorganic tin salts is 1：(1.5~3)；
2) above-mentioned mixed liquor is transferred in water heating kettle, it is anti-in 150~180 DEG C that water heating kettle then is placed in into hydro-thermal reaction instrument Answer 6~24h, reaction to cool to room temperature with the furnace after terminating, then, the powder of black obtained with absolute ethyl alcohol cyclic washing, centrifugation, Isolated powder drying is obtained into SnSe2- graphene oxide compound, the mass fraction of Graphene is 10% in compound ~30%.
As a further improvement on the present invention, step 1) in, described inorganic tin salts are SnCl2·2H2O。
As a further improvement on the present invention, step 1) in, concentration of the graphene oxide in solution A is 1~2mg mL-1。
As a further improvement on the present invention, step 1) in, ethanol and the volume ratio of oleyl amine are 1 in solution C:(1~3).
As a further improvement on the present invention, step 1) in, the ultrasonic disperse time is 40~120min.
As a further improvement on the present invention, step 1) in, it is magnetic agitation to stir, and mixing speed is 500~800r/ Min, 1~6h of mixing time.
As a further improvement on the present invention, step 2) in, the compactedness of the water heating kettle is controlled 20~70%.
As a further improvement on the present invention, step 1) specifically include following steps：
1) 8~80mg graphene oxides are added in 8~40mL ethanol, ultrasonic disperse obtains solution A；Weigh 0.0316 ~4.74g selenium powders are added in 2~10mL hydrazine hydrates, and stirring obtains claret solution B；Weigh 0.045~3.865g SnCl2·2H2O is added to 4~8mL ethanol until completely dissolved, is added dropwise over 6~24mL oleyl amines, forms solution C；Then distinguish Solution C and solution B are added dropwise to form mixed solution in solution A, and it is uniform to be placed on magnetic agitation.
As a further improvement on the present invention, prepared SnSe2In-graphene oxide compound, SnSe2For one kind by The flower type structure that thin slice is assembled into, SnSe2The uniform surface for being grown in Graphene.
Relative to prior art, beneficial effects of the present invention are embodied in：
The present invention using ethanol as solvent, inorganic tin salts as Xi Yuan, hydrazine hydrate as reducing agent, using a simple step Solvent-thermal method has prepared the SnSe of pure phase2- graphene oxide compound, and SnSe2It is a kind of flower-shaped knot assembled by six square pieces Structure, hydrazine hydrate can not only reduce selenium powder as reducing agent, there is provided Se2-, and can be with the oxygen-containing official on redox graphene Can roll into a ball, further improve the electric conductivity of Graphene in composite, on the other hand, a certain amount of oleyl amine of present invention addition can Effectively and Sn2+Complexing, controls the size of product, and nanosizing material is more effective for lifting chemical property.In addition, The preparation method that the present invention is used is simple, and repeatability is high, adds graphene oxide by substantially increasing SnSe after hydro-thermal reaction2 The electric conductivity of based composites, structural stability, it is contemplated that there is preferable chemical property as lithium/sodium ion electrode material.
【Brief description of the drawings】
Fig. 1 is the SnSe prepared by embodiment 12X-ray diffraction (XRD) collection of illustrative plates of-graphene oxide composite material；
Fig. 2 is the SnSe prepared by embodiment 12ESEM (SEM) photo of-graphene oxide composite material.
【Specific embodiment】
The present invention is elaborated with reference to the accompanying drawings and examples.
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound, including：
1) 20~80mg graphene oxides are added in 8~40mL ethanol, 40~120min of ultrasonic disperse obtains solution A；Weigh 0.0316~4.74g selenium powders to be added in 2~10mL hydrazine hydrates, 20~60min of stirring obtains claret solution B；Claim Take 0.045~3.865g SnCl2·2H2O is added to 4~8mL ethanol until completely dissolved, is added dropwise over 6~24mL oleyl amines, shape Into solution C；Then solution C and solution B be added dropwise to respectively form mixed solution in solution A, and be placed on magnetic force and stirred Mix and 20~40min is stirred with the speed of 500~800r/min on machine.Graphene oxide concentration in ethanol is 1~2mg mL-1.Ethanol and the volume ratio of oleyl amine are 1 in solution C:(1~3).
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 6~24h is reacted in 150~180 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then, anti-with absolute ethyl alcohol After backwashing is washed 3~6 times and the powder for obtaining black is centrifuged, and isolated powder drying is obtained into SnSe2- graphene oxide is combined Thing.
The step 2) in, the compactedness of the water heating kettle is controlled 20~70%.
Prepared SnSe2In-graphene oxide compound, SnSe2It is a kind of flower type structure being assembled into by thin slice piece, SnSe2The uniform surface for being grown in Graphene.
Embodiment 1
1) 20mg graphene oxides are added in 10mL ethanol, ultrasonic disperse 60min obtains solution A；Weigh 0.21g selenium Powder is added in 3mL hydrazine hydrates, and stirring 20min obtains claret solution B；Weigh 0.15g SnCl2·2H2O is added to 5mL second Alcohol until completely dissolved, is added dropwise over 12mL oleyl amines, forms solution C；Then solution C and solution B be added dropwise to respectively molten Mixed solution is formed in liquid A, and is placed on magnetic stirrer with the speed stirring 30min of 500r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 24h are reacted in 160 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then with absolute ethyl alcohol cyclic washing 6 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
3) sample (SnSe is analyzed with Rigaku D/max2000PCX- x ray diffractometer xs2- graphene oxide compound), It was found that sample numbers the SnSe of the hexagonal crystal system for being 89-3197 with JCPDS2Structure is consistent, but does not find the diffraction of Graphene Peak, it may be possible to which Graphene peak is not weaker substantially caused.The sample is seen with field emission scanning electron microscope (FESEM) Examine, it can be seen that prepared SnSe2SnSe in-graphene oxide compound2It is a kind of flower type structure being assembled into by piece, The even surface for being grown in Graphene.
Embodiment 2
1) 20mg graphene oxides are added in 20mL ethanol, ultrasonic disperse 40min obtains solution A；Weigh 0.42g selenium Powder is added in 2mL hydrazine hydrates, and stirring 30min obtains claret solution B；Weigh 0.225g SnCl2·2H2O is added to 4mL second Alcohol until completely dissolved, is added dropwise over 6mL oleyl amines, forms solution C；Then solution C and solution B are added dropwise to solution respectively Mixed solution is formed in A, and is placed on magnetic stirrer with the speed stirring 20min of 800r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 12h are reacted in 180 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then with absolute ethyl alcohol cyclic washing 6 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
Embodiment 3
1) 40mg graphene oxides are added in 30mL ethanol, ultrasonic disperse 90min obtains solution A；Weigh 1.26g selenium Powder is added in 5mL hydrazine hydrates, and stirring 60min obtains claret solution B；Weigh 0.85g SnCl2·2H2O is added to 5mL second Alcohol until completely dissolved, is added dropwise over 5mL oleyl amines, forms solution C；Then solution C and solution B are added dropwise to solution respectively Mixed solution is formed in A, and is placed on magnetic stirrer with the speed stirring 40min of 600r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 10h are reacted in 170 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then with absolute ethyl alcohol cyclic washing 6 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
Embodiment 4
1) 60mg graphene oxides are added in 30mL ethanol, ultrasonic disperse 120min obtains solution A；Weigh 0.252g Selenium powder is added in 6mL hydrazine hydrates, and stirring 40min obtains claret solution B；Weigh 0.198g SnCl2·2H2O is added to 4mL Ethanol until completely dissolved, is added dropwise over 8mL oleyl amines, forms solution C；Then solution C and solution B be added dropwise to respectively molten Mixed solution is formed in liquid A, and is placed on magnetic stirrer with the speed stirring 30min of 700r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 24h are reacted in 150 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then with absolute ethyl alcohol cyclic washing 6 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
Embodiment 5
1) 20mg graphene oxides are added in 15mL ethanol, ultrasonic disperse 100min obtains solution A；Weigh 1.785g Selenium powder is added in 8mL hydrazine hydrates, and stirring 50min obtains claret solution B；Weigh 0.975g SnCl2·2H2O is added to 8mL Ethanol until completely dissolved, is added dropwise over 10mL oleyl amines, forms solution C；Then solution C and solution B are added dropwise to respectively Mixed solution is formed in solution A, and is placed on magnetic stirrer with the speed stirring 50min of 800r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 18h are reacted in 180 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then with absolute ethyl alcohol cyclic washing 6 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
Embodiment 6
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound, including：
1) 8mg graphene oxides are added in 8mL ethanol, ultrasonic disperse 40min obtains solution A；Weigh 0.0316g selenium Powder is added in 2mL hydrazine hydrates, and stirring 20min obtains claret solution B；Weigh 0.045g SnCl2·2H2O is added to 4mL second Alcohol until completely dissolved, is added dropwise over 6mL oleyl amines, forms solution C；Then solution C and solution B are added dropwise to solution respectively Mixed solution is formed in A, and is placed on magnetic stirrer with the speed stirring 20min of 500r/min.Graphene oxide exists Concentration in ethanol is 1mgmL-1。
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 6h are reacted in 150 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then, with absolute ethyl alcohol cyclic washing 3 times Centrifugation obtains the powder of black, and isolated powder drying is obtained into SnSe2- graphene oxide compound.
Embodiment 7
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound, including：
1) 80mg graphene oxides are added in 40mL ethanol, ultrasonic disperse 120min obtains solution A；Weigh 4.74g Selenium powder is added in 10mL hydrazine hydrates, and stirring 60min obtains claret solution B；Weigh 3.865g SnCl2·2H2O is added to 8mL ethanol until completely dissolved, is added dropwise over 24mL oleyl amines, forms solution C；Then solution C and solution B are added dropwise over respectively Mixed solution is formed in solution A, and is placed on magnetic stirrer with the speed stirring 40min of 800r/min.Oxidation stone Black alkene concentration in ethanol is 2mgmL-1。
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettles, then puts polytetrafluoroethylene (PTFE) water heating kettle 24h is reacted in 180 DEG C in hydro-thermal reaction instrument, reaction cools to room temperature with the furnace after terminating, then, with absolute ethyl alcohol cyclic washing 6 It is secondary that the powder for obtaining black is centrifuged, isolated powder drying is obtained into SnSe2- graphene oxide compound.
In a word, the present invention is prepared for the SnSe of pure phase using a step solvent-thermal method using ethanol as solvent2- graphite oxide Alkene compound, wherein SnSe2It is a kind of bouquet being assembled into by six square pieces, and is uniformly grown in the surface of Graphene.This hair Bright preparation method is simple, cycle is short, and using Graphene as matrix, not only increases SnSe2Electric conductivity, and improve The structural stability of composite, it is contemplated that the composite as catalysis material and electrode material, with preferable photocatalysis And chemical property.

Claims (9)

1. a kind of solvent-thermal method prepares flower-shaped SnSe2The method of-graphene oxide compound, it is characterised in that：Including following step Suddenly：
1) add graphene oxide into ethanol, ultrasonic disperse obtains solution A；Take selenium powder to be added in hydrazine hydrate, stirring is equal It is even to obtain claret solution B；Take inorganic tin salts and be added to ethanol until completely dissolved, be added dropwise over oleyl amine, form solution C；So Solution C and solution B be added dropwise to respectively afterwards to form mixed solution in solution A, and stirred；In solution selenium powder with it is inorganic The mol ratio of pink salt is 1：(1.5~3)；
2) above-mentioned mixed liquor is transferred in water heating kettle, water heating kettle then is placed in into hydro-thermal reaction instrument reacts 6 in 150~180 DEG C ~24h, reaction cools to room temperature with the furnace after terminating, and then, the powder of black is obtained with absolute ethyl alcohol cyclic washing, centrifugation, will Isolated powder drying obtains SnSe2- graphene oxide compound, in compound the mass fraction of Graphene be 10%~ 30%.
2. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) in, described inorganic tin salts are SnCl2·2H2O。
3. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) in, concentration of the graphene oxide in solution A is 1~2mgmL-1。
4. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) in, ethanol and the volume ratio of oleyl amine are 1 in solution C:(1~3).
5. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) in, the ultrasonic disperse time is 40~120min.
6. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) in, it is magnetic agitation to stir, and mixing speed is 500~800r/min, 1~6h of mixing time.
7. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 2) in, the compactedness of the water heating kettle is controlled 20~70%.
8. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Step 1) specifically include following steps：
1) 8~80mg graphene oxides are added in 8~40mL ethanol, ultrasonic disperse obtains solution A；Weigh 0.0316~ 4.74g selenium powders are added in 2~10mL hydrazine hydrates, and stirring obtains claret solution B；Weigh 0.045~3.865g SnCl2· 2H2O is added to 4~8mL ethanol until completely dissolved, is added dropwise over 6~24mL oleyl amines, forms solution C；Then respectively by solution C and solution B are added dropwise to form mixed solution in solution A, and it is uniform to be placed on magnetic agitation.
9. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of-graphene oxide compound, its feature It is：Prepared SnSe2In-graphene oxide compound, SnSe2It is a kind of flower type structure being assembled into by thin slice, SnSe2 The uniform surface for being grown in Graphene.
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CN108163820A (en) * 2018-03-09 2018-06-15 太原理工大学 A kind of method of low temperature preparation tin diselenide nano line
CN108400305A (en) * 2018-03-01 2018-08-14 中国科学院福建物质结构研究所 A kind of carbon packet SnSe2Composite material and preparation method and application
CN108588838A (en) * 2018-03-23 2018-09-28 桂林电子科技大学 A method of preparing the SnSe polycrystalline bulks with high thermoelectricity capability
CN109473643A (en) * 2018-10-17 2019-03-15 长沙学院 A kind of CoSe2/ graphene composite material preparation method and purposes
CN109521063A (en) * 2018-12-04 2019-03-26 海南聚能科技创新研究院有限公司 The nitrogen dioxide gas sensor of petal-shaped SnSe2
CN112490429A (en) * 2020-12-03 2021-03-12 上海汉行科技有限公司 Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof
CN113097485A (en) * 2021-04-01 2021-07-09 陕西科技大学 Sandwich-like structure SnSe/r-GO compound and preparation method and application thereof

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CN107437615A (en) * 2017-07-05 2017-12-05 东莞中汽宏远汽车有限公司 High-capacity lithium battery negative pole and preparation method thereof and lithium battery
CN108400305A (en) * 2018-03-01 2018-08-14 中国科学院福建物质结构研究所 A kind of carbon packet SnSe2Composite material and preparation method and application
CN108400305B (en) * 2018-03-01 2021-06-22 中国科学院福建物质结构研究所 Carbon-coated SnSe2Composite material and preparation method and application thereof
CN108163820A (en) * 2018-03-09 2018-06-15 太原理工大学 A kind of method of low temperature preparation tin diselenide nano line
CN108163820B (en) * 2018-03-09 2021-10-26 太原理工大学 Method for preparing tin diselenide nanowire at low temperature
CN108588838B (en) * 2018-03-23 2019-12-06 桂林电子科技大学 method for preparing SnSe polycrystalline block with high thermoelectric performance
CN108588838A (en) * 2018-03-23 2018-09-28 桂林电子科技大学 A method of preparing the SnSe polycrystalline bulks with high thermoelectricity capability
CN109473643A (en) * 2018-10-17 2019-03-15 长沙学院 A kind of CoSe2/ graphene composite material preparation method and purposes
CN109473643B (en) * 2018-10-17 2021-06-25 长沙学院 CoSe2Preparation method and application of graphene composite material
CN109521063A (en) * 2018-12-04 2019-03-26 海南聚能科技创新研究院有限公司 The nitrogen dioxide gas sensor of petal-shaped SnSe2
CN112490429A (en) * 2020-12-03 2021-03-12 上海汉行科技有限公司 Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof
CN112490429B (en) * 2020-12-03 2023-06-13 上海汉行科技有限公司 Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof
CN113097485A (en) * 2021-04-01 2021-07-09 陕西科技大学 Sandwich-like structure SnSe/r-GO compound and preparation method and application thereof

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