CN108190864A - A kind of graphene preparation method - Google Patents
A kind of graphene preparation method Download PDFInfo
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- CN108190864A CN108190864A CN201810038099.2A CN201810038099A CN108190864A CN 108190864 A CN108190864 A CN 108190864A CN 201810038099 A CN201810038099 A CN 201810038099A CN 108190864 A CN108190864 A CN 108190864A
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Abstract
The present invention relates to technical field of graphene preparation, and in particular to a kind of graphene preparation method.The present invention uses low-cost liquid metal tin as carrier, and using carbohydrate as solid-state carbon source, by high-temperature digestion carbon atom, and the solid metallic tin to be formed after cooling generates graphene as substrate.Compared with solid phase method particularly mechanical stripping method, method provided by the present invention can effectively control the carbon atom number of plies of generated graphene by controlling the addition of solid-state carbon source；Compared with liquid phase method, the present invention is during graphene is prepared and the poisonous and hazardous hazardous chemical such as strong acid, highly basic is not used, and eliminates liquid phase method and prepares waste treatment process after graphene；Compared with vapor phase method, metallic tin used in the present invention is lower than monocrystalline nickel and copper foil cost, and the present invention substitutes gaseous carbon source with solid-state carbon source, and it reduce the technology difficulties in graphene preparation process.
Description
Technical field
The present invention relates to technical field of graphene preparation, and in particular to a kind of graphene preparation method.
Background technology
According to carbon source form and the difference of reaction medium, the method for preparing graphene can substantially be divided into solid phase method, gas phase
Method and liquid phase method three categories.
Solid phase method refers to a kind of method that the carbon source of growth graphene supplies in solid form, and presence can not accurately control
The number of plies of graphene and it is less efficient the problem of.Such as mechanical stripping method.Mechanical stripping method be Geim in 2004 et al. for the first time into
The method that graphene platelet is made in work(.This method is easy to operate, can prepare the graphene of the higher small size of mass, fits
It prepares graphene on a small scale together in laboratory and is used as research.But this method takes longer, to obtain graphene solution concentration pole
It is low, and the number of plies of obtained graphene can not be accurately controlled, it is less efficient.In addition, single-layer graphene is mixed with multi-layer graphene
It is combined, is not easy to the selection of single-layer graphene.So mechanical stripping method cannot be used for scale and industrialized production.
Liquid phase method is one of the effective ways for obtaining high-quality graphene, it uses toxic, explosive hazardous chemical,
The cost of liquid waste processing is not only increased, the subsequent applications of graphene but will be brought a negative impact, limit it in microelectronics
Application in device.Such as oxidation-reduction method：2006, the Ruoff team research of Texas ,Usa university Austin
Hydrazine hydrate reduction graphite oxide alkene reaction.Then, it has been found that reduced sugar (glucose, fructose, sucrose), vitamin C are to oxygen
Graphite alkene also has certain reproducibility.Graphene oxidation-reduction method is of low cost and easy to operate, is to prepare stone on a large scale
The alternative of black alkene, however this method often leads to graphite-structure during graphene oxide and generates defect, and restore
Modification group can be left in graphene because of the imperfection of reaction again in the process, these can all produce the performance of graphene
Raw negative effect.Since grapheme material has the specific surface area of superelevation, cause in the preparation process of grapheme material easily
Agglomeration occurs.In addition, reducing agent hydrazine hydrate, sodium borohydride etc. that chemical reduction method uses all are toxic, explosive danger
Chemicals not only increases the cost of liquid waste processing, and the subsequent applications of graphene but will be brought a negative impact, limit its
Application in microelectronic component.
Vapor phase method refers to grow a kind of method of graphene in gaseous state or plasma state, and there are high costs and technique to answer
It is miscellaneous to spend the problem of high.Such as chemical vapour deposition technique (CVD)：Chemical vapour deposition technique is with energy (thermal energy, radio frequency, plasma
Body etc.) exciting gas reactant and bring it about chemical reaction, and formed on deposited substrate surface it is fine and close, uniformly, it is steady
A kind of chemical film growth techniques of fixed solid film.This method production technology is perfect, ripe, Recent study personnel's handle
The approach that it is prepared as graphene.South Korea was successfully prepared into Hong of Jun Guan universities etc. in 2009 using CVD method
The graphene of better quality.It is preferable as its although large area and the high graphene of quality can be prepared with CVD method
The monocrystalline nickel of depositing base material is very expensive, and the graphene crystallite dimension grown is smaller, and the number of plies is uneven and uncontrollable,
Therefore this method is not appropriate for carrying out industrialization promotion.Equally in 2009, Texas ,Usa university Austin
Ruoff team prepares the large-area graphene based on individual layer by the use of copper foil as matrix, and react have it is good can
Control property.However chemical deposition prepares the approach of graphene and also explores, improves further, at this stage technique it is immature with
And higher equipment requirement and cost all limit its large-scale application.And such method is also needed using gaseous carbon source, this
Requirement of the technological means to consersion unit is high, so as to increase process complexity.
Invention content
For the various deficiencies of existing graphene preparation technology, the number of plies of graphene can not be accurately controlled to solve solid phase method
With size and less efficient；Toxic in liquid phase method, explosive hazardous chemical, to the subsequent applications of graphene, there are negative shadows
It rings；And the technical issues of high cost existing for vapor phase method and technology difficulty.The present invention provides a kind of graphene preparation method,
Comprehensively utilize liquid, the method for solid two condition substance carries out graphene preparation.
Specific technical solution is as follows：
Tin is placed in 40~100 DEG C waters and cleans by step 1, is then cleaned using organic solvent, then dry up.
Step 2, step 1 is cleaned after tin and solid-state carbon source the 0.1-1wt ‰ of gross mass both is accounted for by carbon, be placed in reaction
In device；Reactor is placed in tube furnace, then is passed through argon gas to tube furnace and reactor, argon flow amount is 500~1500mL/
Min, to exclude the air in tube furnace and reactor, there are one receive container in tube furnace.
Step 3 keeps argon gas atmosphere, is passed through in hydrogen to reactor, and hydrogen flowing quantity is 50~200mL/min, with 5~10
DEG C/heating of the speed of min, final temperature is maintained at 1000 DEG C~2000 DEG C, then constant temperature keeps 20~60min.
Step 4 reduces argon flow amount to 50~100mL/min, and the valve of closing tube furnace end within half a minute will be anti-
The liquid tin of 1/5-1/3 in device is answered to extrude reactor to receiving container；Then valve is opened with pressure in balanced reaction device, is made anti-
Liquid tin in device is answered no longer to extrude.
Step 5 continues to be passed through 50~100mL/min of argon gas, stops heating, etc. temperature drop to after room temperature close argon gas and
Hydrogen takes out and receives container, will receive the mix products of metallic tin and graphene in container and carries out cleaning separation, you can obtains most
Whole graphene.
Preferably, organic solvent is ethyl alcohol, acetone and/or isopropanol in the step 1.
Preferably, carbon source is fructose, glucose and/or sucrose in the step 2.
The present invention uses low-cost liquid metal tin, using carbohydrate cheap and easy to get as solid-state carbon source, to pass through for carrier
High-temperature digestion carbon atom, and the solid metallic tin to be formed after cooling generates graphene as substrate.It is particularly mechanical with solid phase method
Stripping method is compared, and method provided by the present invention effectively can control generated graphite by controlling the addition of solid-state carbon source
The carbon atom number of plies of alkene；Compared with liquid phase method, the present invention is during graphene is prepared and is not used that strong acid, highly basic etc. are toxic to be had
Harmful hazardous chemical eliminates liquid phase method and prepares waste treatment process after graphene；Compared with vapor phase method, institute of the present invention
The metallic tin used is lower than monocrystalline nickel and copper foil cost, and the present invention substitutes gaseous carbon source with solid-state carbon source, it reduce
Technology difficulty in graphene preparation process.
Description of the drawings
Fig. 1 is the structure diagram of embodiment graphene preparation facilities；
Reference numeral：1- adjusts flowmeter, 2- valves, 3- valves, 4- tube furnaces, 5- reception containers, 6- reactors, 7- valves
Door, 8- spark arrester devices.
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and examples.
Graphene is prepared using device as shown in Figure 1.Argon gas, hydrogen and carbon source acetylene are controlled by flowmeter and valve
Inflow and flow；Reacting environment and required is provided the dissolving of carbon atom by fusing of the tube furnace for metallic tin and liquid tin
High temperature；Have reactor in tube furnace and receive container, wherein the reactor of lower wind direction be under high-temperature condition metallic tin fusing with
And the place of liquid tin dissolving carbon atom, the reception container of upwind be in temperature-fall period carbon atom be precipitated from liquid tin and
The place that graphene is formed.By the valve of tube furnace end, the air pressure in closed reactor and the transfer of liquid tin are controlled.
The last of tube furnace has installed the spark arrester for preventing fire additional.Wherein reactor 6 is closed container, and reception container 5 is open-top receptacle.
This method is passed through argon gas to generate needed for reaction in the case where opening all three valves before heating is reacted
Atmosphere of inert gases, and all keep argon gas atmosphere in entire reaction process.Heating start after, be passed through hydrogen ensure tube furnace and
Reproducibility atmosphere in reactor.Treat that the mixture of metallic tin and solid-state carbon source is melted and kept the temperature.After reaction, argon gas is reduced
To 50~100mL/min of intake, the valve of tube furnace end is closed within half a minute.Using argon gas in downstream reactor
The pressure of generation receives wherein carbon containing liquid metal tin press-in upstream in container.In cooling procedure, upstream receives container
It fully relies on the carbon being precipitated in liquid metal tin and generates graphene.
Reaction carries out at high temperature, and needs to be passed through the imflammable gas such as hydrogen, therefore can be at tubular type furnace apparatus end
End is connected into spark arrester device, to prevent the reactor damage that the burning of gas during the reaction causes, ensures that experiment safety carries out.
As shown in Figure 1, the operating procedure that the present embodiment prepares graphene is as follows：
Block tin is placed in 40 DEG C waters and is cleaned by ultrasonic 30min by step 1, and block tin is rinsed with deionized water, and in second
It is cleaned by ultrasonic 3 times, time 5min in alcohol, nitrogen drying.
Step 2, step 1 is cleaned after block tin and glucose the 0.5wt ‰ of gross mass both is accounted for by carbon, be placed in reactor
In；Reactor is placed in tube furnace, then is passed through argon gas to tube furnace and reactor, argon flow amount 1000mL/min, with row
Except the air in tube furnace and reactor, there are one receive container in tube furnace.
Step 3 keeps argon gas atmosphere, is passed through in hydrogen to reactor, hydrogen flowing quantity 100mL/min, with 10 DEG C/min
Speed heating, final temperature is maintained at 1000 DEG C, then constant temperature keeps 30min.
Step 4 reduces argon flow amount to 100mL/min, the valve of tube furnace end is closed within half a minute, by reactor
In 1/3 liquid tin extrude reactor to receiving container；Then valve is opened with pressure in balanced reaction device, makes liquid in reactor
State tin no longer extrudes.
Step 5 continues to be passed through the argon gas of 100mL/min, stops heating, etc. temperature drop to room temperature after close argon gas and hydrogen
Gas takes out and receives container, will receive the mix products of metallic tin and graphene in container and carries out cleaning separation, you can obtains final
Graphene.
Claims (3)
1. a kind of graphene preparation method, is as follows：
Tin is placed in 40~100 DEG C waters and cleans by step 1, is then cleaned using organic solvent, then dry up；
Step 2, step 1 is cleaned after tin and solid-state carbon source the 0.1-1wt ‰ of gross mass both is accounted for by carbon, be placed in reactor
In；Reactor is placed in tube furnace, then is passed through argon gas to tube furnace and reactor, argon flow amount is 500~1500mL/min,
To exclude the air in tube furnace and reactor, there are one receive container in tube furnace；
Step 3, keep argon gas atmosphere, be passed through in hydrogen to reactor, hydrogen flowing quantity be 50~200mL/min, with 5~10 DEG C/
The speed heating of min, final temperature are maintained at 1000 DEG C~2000 DEG C, then constant temperature keeps 20~60min；
Step 4 reduces argon flow amount to 50~100mL/min, the valve of tube furnace end is closed within half a minute, by reactor
The liquid tin of middle 1/5-1/3 extrudes reactor to receiving container；Then valve is opened with pressure in balanced reaction device, makes reactor
Middle liquid tin no longer extrudes；
Step 5 continues to be passed through 50~100mL/min of argon gas, stops heating, etc. temperature drop to room temperature after close argon gas and hydrogen
Gas takes out and receives container, will receive the mix products of metallic tin and graphene in container and carries out cleaning separation, you can obtains final
Graphene.
2. graphene preparation method as described in claim 1, it is characterised in that：Organic solvent is ethyl alcohol, acetone in the step 1
And/or isopropanol.
3. graphene preparation method as described in claim 1, it is characterised in that：Carbon source is fructose, glucose in the step 2
And/or sucrose.
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Citations (8)
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| CN102011100A (en) * | 2010-12-01 | 2011-04-13 | 中国科学院化学研究所 | Method for preparing large-area high quality graphene on iron-based substrate |
| WO2011112598A1 (en) * | 2010-03-08 | 2011-09-15 | William Marsh Rice University | Growth of graphene films from non-gaseous carbon sources |
| CN102392225A (en) * | 2011-07-22 | 2012-03-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanoribbon on insulating substrate |
| CN102583359A (en) * | 2012-04-01 | 2012-07-18 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene by adopting liquid catalyst aided chemical vapor deposition |
| CN103086359A (en) * | 2011-11-01 | 2013-05-08 | 海洋王照明科技股份有限公司 | Method for continuously preparing graphene |
| US20150023860A1 (en) * | 2013-07-19 | 2015-01-22 | Nanomaterial Innovation Ltd. | Graphene-like nanosheet structure network on a substrate and the method for forming the same |
| CN104498892A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing graphene film through low-temperature fixed-point nucleating |
| CN107128904A (en) * | 2017-05-11 | 2017-09-05 | 张丽慧 | A kind of method that metal catalytic prepares graphene |
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2018
- 2018-01-16 CN CN201810038099.2A patent/CN108190864B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011112598A1 (en) * | 2010-03-08 | 2011-09-15 | William Marsh Rice University | Growth of graphene films from non-gaseous carbon sources |
| CN102011100A (en) * | 2010-12-01 | 2011-04-13 | 中国科学院化学研究所 | Method for preparing large-area high quality graphene on iron-based substrate |
| CN102392225A (en) * | 2011-07-22 | 2012-03-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanoribbon on insulating substrate |
| CN103086359A (en) * | 2011-11-01 | 2013-05-08 | 海洋王照明科技股份有限公司 | Method for continuously preparing graphene |
| CN102583359A (en) * | 2012-04-01 | 2012-07-18 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene by adopting liquid catalyst aided chemical vapor deposition |
| US20150023860A1 (en) * | 2013-07-19 | 2015-01-22 | Nanomaterial Innovation Ltd. | Graphene-like nanosheet structure network on a substrate and the method for forming the same |
| CN104498892A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing graphene film through low-temperature fixed-point nucleating |
| CN107128904A (en) * | 2017-05-11 | 2017-09-05 | 张丽慧 | A kind of method that metal catalytic prepares graphene |
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