CN106784678B - 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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CN106784678B
CN106784678B CN201611180010.3A CN201611180010A CN106784678B CN 106784678 B CN106784678 B CN 106784678B CN 201611180010 A CN201611180010 A CN 201611180010A CN 106784678 B CN106784678 B CN 106784678B
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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 process is as follows: first dispersing graphene oxide spare in ethanol, a certain amount of selenium powder is then added in hydrazine hydrate dissolution and forms claret solution, then by a certain amount of SnCl2·2H2O, which dissolves in ethanol and oleyl amine is added dropwise, forms mixed solution, finally the mixed liquor and above-mentioned claret solution are added dropwise in the mixed solution of graphene respectively, it is transferred in water heating kettle at 150~180 DEG C heat preservation 6~for 24 hours after mixing evenly, collects precipitating and obtains SnSe2With the compound of graphene.The preparation process that the present invention uses is simple, and the appearance and size of product is controllable, and repeatability is high, and greatly improves SnSe2The electric conductivity of sill has 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 SnSe2A kind of preparation method of graphene oxide compound, and in particular to solvent-thermal method preparation flower Shape SnSe2The method of graphene oxide compound.
[background technique]
Stannic selenide is a kind of important semiconductor material, and its rich content, environmental-friendly, chemical property are stablized, because
And have an important application at many aspects, especially resistance-variable storing device, infrared electro device, solar battery and Lithium ion battery etc..In recent years, it is even more had become a hot topic of research as lithium ion/sodium-ion battery negative electrode material, but To there is document report to point out, stannic selenide as negative electrode material although theoretical capacity with higher, itself lower electronics/from Electron conductivity, and biggish volume expansion strong influence chemical property during embedding lithium/sodium, so that charge and discharge capacitor Measure rapid decay.
In order to improve the electronic conductivity of stannic selenide, alleviate volume expansion, many researchers answer stannic selenide and carbon It closes, on the one hand improves the electric conductivity of composite material, another aspect carbon can be alleviated to a certain extent as matrix to discharge The volume expansion problem of journey.Zhian Zhang etc. is using tin and selenium powder as raw material, and conductive black is as carbon source, using ball milling Method is prepared for the composite material of stannic selenide and carbon as lithium/sodium-ion battery cathode, improves composite wood 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 Stannic selenide nanoparticle growth will be made to substantially increase composite wood in the inside of carbon fiber Deng the method by ball milling power-up deposition The structural stability of material alleviates volume 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, is being aoxidized using the nanometer tin selenide homoepitaxial that hydro-thermal method and subsequent calcination are prepared for sheet-like morphology The anode material of graphene surface shows excellent chemical property (Zhang Zhi as anode material of lithium-ion battery Peace, Zhao Xingxing, Juan etc., a kind of stannic selenide for sodium-ion battery/graphene oxide anode material and its preparation side Method, China Patent No.: 201510046305.0).
It can be seen that the really a kind of effective means that improve stannic selenide chemical property compound with carbon.But The preparation method reported at present, the relatively complicated complexity of process, even with Large expensive equipment.Therefore, a kind of prepare is developed Method is simple, and the method for capableing of Effective Regulation product structure is particularly important.
[summary of the invention]
The purpose of the present invention is to provide a kind of solvent-thermal methods to prepare flower-shaped SnSe2The method of graphene oxide compound, Prepared SnSe2Graphene oxide compound is the SnSe of flower-like structure2Uniformly it is grown in the surface of graphene, knot Structure stability, it is contemplated that there is preferable chemical property as lithium/sodium ion electrode material.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound, comprising the following steps:
1) it adds graphene oxide into ethyl alcohol, ultrasonic disperse obtains solution A；It takes selenium powder to be added in hydrazine hydrate, stirs It mixes and uniformly obtains claret solution B；It takes inorganic tin salts to be added to ethyl alcohol until completely dissolved, oleyl amine is added dropwise, form solution C；Then solution C and solution B are added dropwise in solution A respectively and form mixed solution, and stirred evenly；In solution selenium powder with The molar 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 is then placed in hydro-thermal reaction instrument Answer 6~for 24 hours, it cools to room temperature with the furnace after reaction, then, is washed repeatedly with dehydrated alcohol, is centrifuged and obtains the powder of black, It dries isolated powder to obtain SnSe2Graphene oxide compound, the mass fraction of graphene is 10% in compound ~30%.
As a further improvement of the present invention, in step 1), the inorganic tin salts are SnCl2·2H2O。
As a further improvement of the present invention, in step 1), concentration of the graphene oxide in solution A is 1~2mg mL-1。
As a further improvement of the present invention, in step 1), the volume ratio of ethyl alcohol and oleyl amine is 1:(1~3 in solution C).
As a further improvement of the present invention, in step 1), the ultrasonic disperse time is 40~120min.
As a further improvement of the present invention, it in step 1), stirs as magnetic agitation, mixing speed is 500~800r/ Min, 1~6h of mixing time.
As a further improvement of the present invention, in step 2), the compactedness of the water heating kettle is controlled 20~70%.
As a further improvement of the present invention, step 1) specifically includes the following steps:
1) 8~80mg graphene oxide is added in 8~40mL ethyl alcohol, ultrasonic disperse obtains solution A；Weigh 0.0316 ~4.74g selenium powder is added in 2~10mL hydrazine hydrate, stirs to get claret solution B；Weigh 0.045~3.865g SnCl2·2H2O is added to 4~8mL ethyl alcohol until completely dissolved, and 6~24mL oleyl amine is added dropwise, and forms solution C；Then divide Solution C and solution B are not added dropwise in solution A and form mixed solution, and it is uniform to place it in magnetic agitation.
As a further improvement of the present invention, prepared SnSe2In graphene oxide compound, SnSe2For one kind by The flower type structure that thin slice is assembled into, SnSe2Uniformly it is grown in the surface of graphene.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
The present invention is using ethyl alcohol as solvent, and inorganic tin salts are as tin source, and hydrazine hydrate is as reducing agent, using a simple step Solvent-thermal method has prepared the SnSe of pure phase2Graphene oxide compound, and SnSe2It is a kind of flower-shaped knot assembled by six square pieces Structure, hydrazine hydrate can not only restore selenium powder as reducing agent, provide Se2-, and can be with the oxygen-containing official on redox graphene It can roll into a ball, further increase the electric conductivity of graphene in composite material, on the other hand, a certain amount of oleyl amine is added in the present invention, can Effectively and Sn2+Complexing controls the size of product, and nanosizing material is more effective for promoting chemical property.In addition to this, The preparation method that the present invention uses is simple, and repeatability is high, and graphene oxide is added and substantially increases 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.
[Detailed description of the invention]
Fig. 1 is SnSe prepared by embodiment 12X-ray diffraction (XRD) map of graphene oxide composite material；
Fig. 2 is SnSe prepared by embodiment 12Scanning electron microscope (SEM) photo of graphene oxide composite material.
[specific embodiment]
It elaborates with reference to the accompanying drawings and examples to the present invention.
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound, comprising:
1) 20~80mg graphene oxide is added in 8~40mL ethyl alcohol, 40~120min of ultrasonic disperse obtains solution A；It weighs 0.0316~4.74g selenium powder to be added in 2~10mL hydrazine hydrate, 20~60min of stirring obtains claret solution B；Claim Take 0.045~3.865g SnCl2·2H2O is added to 4~8mL ethyl alcohol until completely dissolved, and 6~24mL oleyl amine is added dropwise, Form solution C；Then solution C and solution B are added dropwise in solution A respectively and form mixed solution, and place it in magnetic force 20~40min is stirred with the speed of 500~800r/min on blender.The concentration of graphene oxide in ethanol is 1~2mg mL-1.The volume ratio of ethyl alcohol and oleyl amine is 1:(1~3 in solution C).
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle In hydro-thermal reaction instrument in 150~180 DEG C react 6~for 24 hours, cool to room temperature with the furnace after reaction, it is then, anti-with dehydrated alcohol After backwashing washs 3~6 centrifugations and obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide is compound Object.
In the step 2), the compactedness of the water heating kettle is controlled 20~70%.
Prepared SnSe2In graphene oxide compound, SnSe2For a kind of flower type structure being assembled by thin slice piece, SnSe2Uniformly it is grown in the surface of graphene.
Embodiment 1
1) 20mg graphene oxide is added in 10mL ethyl alcohol, ultrasonic disperse 60min obtains solution A；Weigh 0.21g Selenium powder is added in 3mL hydrazine hydrate, and stirring 20min obtains claret solution B；Weigh 0.15g SnCl2·2H2O is added to 5mL Until completely dissolved, 12mL oleyl amine is added dropwise in ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise to respectively Mixed solution is formed in solution A, and places it on magnetic stirrer and 30min is stirred with the speed of 500r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle It is reacted for 24 hours in hydro-thermal reaction instrument in 160 DEG C, cools to room temperature with the furnace after reaction, then washed repeatedly with dehydrated alcohol 6 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
3) sample (SnSe is analyzed with Rigaku D/max2000PCX- x ray diffractometer x2Graphene oxide compound), It was found that the SnSe for the hexagonal crystal system that sample and JCPDS number are 89-31972Structure is consistent, but does not find the diffraction of graphene Peak, it may be possible to which graphene peak is weaker unobvious caused.The sample is seen with field emission scanning electron microscope (FESEM) It examines, it can be seen that prepared SnSe2SnSe in graphene oxide compound2For a kind of flower type structure being assembled by piece, The even surface for being grown in graphene.
Embodiment 2
1) 20mg graphene oxide is added in 20mL ethyl alcohol, ultrasonic disperse 40min obtains solution A；Weigh 0.42g Selenium powder is added in 2mL hydrazine hydrate, and stirring 30min obtains claret solution B；Weigh 0.225g SnCl2·2H2O is added to 4mL Until completely dissolved, 6mL oleyl amine is added dropwise in ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise to respectively molten Mixed solution is formed in liquid A, and places it on magnetic stirrer and 20min is stirred with the speed of 800r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle In hydro-thermal reaction instrument in 180 DEG C of reaction 12h, cools to room temperature with the furnace after reaction, then washed repeatedly with dehydrated alcohol 6 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
Embodiment 3
1) 40mg graphene oxide is added in 30mL ethyl alcohol, ultrasonic disperse 90min obtains solution A；Weigh 1.26g Selenium powder is added in 5mL hydrazine hydrate, and stirring 60min obtains claret solution B；Weigh 0.85g SnCl2·2H2O is added to 5mL Until completely dissolved, 5mL oleyl amine is added dropwise in ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise to respectively molten Mixed solution is formed in liquid A, and places it on magnetic stirrer and 40min is stirred with the speed of 600r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle In hydro-thermal reaction instrument in 170 DEG C of reaction 10h, cools to room temperature with the furnace after reaction, then washed repeatedly with dehydrated alcohol 6 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
Embodiment 4
1) 60mg graphene oxide is added in 30mL ethyl alcohol, ultrasonic disperse 120min obtains solution A；Weigh 0.252g Selenium powder is added in 6mL hydrazine hydrate, and stirring 40min obtains claret solution B；Weigh 0.198g SnCl2·2H2O is added to 4mL Until completely dissolved, 8mL oleyl amine is added dropwise in ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise to respectively molten Mixed solution is formed in liquid A, and places it on magnetic stirrer and 30min is stirred with the speed of 700r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle It is reacted for 24 hours in hydro-thermal reaction instrument in 150 DEG C, cools to room temperature with the furnace after reaction, then washed repeatedly with dehydrated alcohol 6 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
Embodiment 5
1) 20mg graphene oxide is added in 15mL ethyl alcohol, ultrasonic disperse 100min obtains solution A；Weigh 1.785g Selenium powder is added in 8mL hydrazine hydrate, and stirring 50min obtains claret solution B；Weigh 0.975g SnCl2·2H2O is added to 8mL Until completely dissolved, 10mL oleyl amine is added dropwise in ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise to respectively Mixed solution is formed in solution A, and places it on magnetic stirrer and 50min is stirred with the speed of 800r/min.
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle In hydro-thermal reaction instrument in 180 DEG C of reaction 18h, cools to room temperature with the furnace after reaction, then washed repeatedly with dehydrated alcohol 6 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
Embodiment 6
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound, comprising:
1) 8mg graphene oxide is added in 8mL ethyl alcohol, ultrasonic disperse 40min obtains solution A；Weigh 0.0316g Selenium powder is added in 2mL hydrazine hydrate, and stirring 20min obtains claret solution B；Weigh 0.045g SnCl2·2H2O is added to Until completely dissolved, 6mL oleyl amine is added dropwise in 4mL ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise respectively Mixed solution is formed into solution A, and places it on magnetic stirrer and 20min is stirred with the speed of 500r/min.Aoxidize stone The concentration of black alkene in ethanol is 1mgmL-1。
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle In hydro-thermal reaction instrument in 150 DEG C of reaction 6h, cools to room temperature with the furnace after reaction, then, washed repeatedly with dehydrated alcohol 3 times Centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
Embodiment 7
A kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound, comprising:
1) 80mg graphene oxide is added in 40mL ethyl alcohol, ultrasonic disperse 120min obtains solution A；Weigh 4.74g Selenium powder is added in 10mL hydrazine hydrate, and stirring 60min obtains claret solution B；Weigh 3.865g SnCl2·2H2O is added to Until completely dissolved, 24mL oleyl amine is added dropwise in 8mL ethyl alcohol, forms solution C；Then solution C and solution B are added dropwise respectively Mixed solution is formed into solution A, and places it on magnetic stirrer and 40min is stirred with the speed of 800r/min.Aoxidize stone The concentration of black alkene in ethanol is 2mgmL-1。
2) above-mentioned mixed liquor is transferred in 100mL polytetrafluoroethylene (PTFE) water heating kettle, then sets polytetrafluoroethylene (PTFE) water heating kettle It is reacted for 24 hours in hydro-thermal reaction instrument in 180 DEG C, cools to room temperature with the furnace after reaction, then, wash 6 repeatedly with dehydrated alcohol Secondary centrifugation obtains the powder of black, dries isolated powder to obtain SnSe2Graphene oxide compound.
In short, using ethyl alcohol as solvent, the SnSe of pure phase is prepared for using a step solvent-thermal method by the present invention2Graphite oxide Alkene compound, wherein SnSe2For a kind of bouquet being assembled by six square pieces, and uniformly it is grown in the surface of graphene.This hair Bright preparation method is simple, and the period is short, and using graphene as matrix, not only increases SnSe2Electric conductivity, and improve The structural stability of composite material, it is contemplated that the composite material has preferable photocatalysis as catalysis material and electrode material And chemical property.

Claims (6)

1. a kind of solvent-thermal method prepares flower-shaped SnSe2The method of graphene oxide compound, it is characterised in that: including following step It is rapid:
1) it adds graphene oxide into ethyl alcohol, ultrasonic disperse obtains solution A；Selenium powder is taken to be added in hydrazine hydrate, stirring is equal It is even to obtain claret solution B；It takes inorganic tin salts to be added to ethyl alcohol until completely dissolved, oleyl amine is added dropwise, form solution C；So Solution C and solution B are added dropwise in solution A respectively afterwards and form mixed solution, and is stirred evenly；In solution selenium powder with it is inorganic The molar ratio of pink salt is 1:(1.5~3)；
2) above-mentioned mixed liquor is transferred in water heating kettle, water heating kettle is then placed in hydro-thermal reaction instrument and reacts 6 in 150~180 DEG C ~for 24 hours, and it cools to room temperature with the furnace after reaction, then, is washed repeatedly with dehydrated alcohol, is centrifuged and obtains the powder of black, it will Isolated powder dries to obtain SnSe2Graphene oxide compound, in compound the mass fraction of graphene be 10%~ 30%；
The inorganic tin salts are SnCl2·2H2O；
The compactedness of the water heating kettle is controlled 20~70%；
Prepared SnSe2In graphene oxide compound, SnSe2For a kind of flower type structure being assembled by thin slice, SnSe2? The even surface for being grown in graphene.
2. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of graphene oxide compound, feature Be: in step 1), concentration of the graphene oxide in solution A is 1~2mgmL-1。
3. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of graphene oxide compound, feature Be: in step 1), the volume ratio of ethyl alcohol and oleyl amine is 1:(1~3 in solution C).
4. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of graphene oxide compound, feature Be: in step 1), the ultrasonic disperse time is 40~120min.
5. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of graphene oxide compound, feature It is: in step 1), stirs as magnetic agitation, mixing speed is 500~800r/min, 1~6h of mixing time.
6. a kind of solvent-thermal method prepares flower-shaped SnSe according to claim 12The method of graphene oxide compound, feature Be: step 1) specifically includes the following steps:
1) 8~80mg graphene oxide is added in 8~40mL ethyl alcohol, ultrasonic disperse obtains solution A；Weigh 0.0316~ 4.74g selenium powder is added in 2~10mL hydrazine hydrate, stirs to get claret solution B；Weigh 0.045~3.865g SnCl2· 2H2O is added to 4~8mL ethyl alcohol until completely dissolved, and 6~24mL oleyl amine is added dropwise, and forms solution C；Then respectively by solution C and solution B, which are added dropwise in solution A, forms mixed solution, and it is uniform to place it in magnetic agitation.
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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
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
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