CN103213979A - Method for preparing graphene by solvent-thermal process - Google Patents
Method for preparing graphene by solvent-thermal process Download PDFInfo
- Publication number
- CN103213979A CN103213979A CN2013101697066A CN201310169706A CN103213979A CN 103213979 A CN103213979 A CN 103213979A CN 2013101697066 A CN2013101697066 A CN 2013101697066A CN 201310169706 A CN201310169706 A CN 201310169706A CN 103213979 A CN103213979 A CN 103213979A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite
- dispersion liquid
- ultrasonic
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing graphene by a solvent-thermal process to overcome the shortcomings of the prior art. The method comprises the following steps of: (1) dispersing expanded graphite or high-purity graphite in an organic solvent under the action of ultrasonic waves to obtain a graphite dispersion solution; (2) placing the graphite dispersion solution in a polytetrafluoroethene high-pressure reaction kettle for acting at high temperature and high pressure to obtain a graphene dispersion solution; and (3) performing further ultrasonic dispersion on the graphene dispersion solution, performing centrifugation, collecting upper-layer liquid, and performing suction filtration and freeze-drying to obtain graphene powder. A scanning electron microscope and a transmission electron microscope are adopted for characterizing the appearance of the graphene; and a Raman spectrum is used for characterizing the defects of the graphene. The results show that the graphene prepared by the method provided by the invention has the advantages of large size, high quality, few defects and the like, and a feasible method is further provided for large-scale application of the graphene.
Description
Technical field
The present invention relates to the method that a kind of solvent-thermal method prepares Graphene.
Background technology
Graphene is another new carbon structural form of being found by scientists after soccerballene, CNT (carbon nano-tube), is by sp
2The hydridization carbon atom bonding, and have the individual layer plane graphite of the cellular two-dirnentional structure of hexagonal lattice.Graphene possesses many special propertys that surmount conventional graphite-raw material of wood-charcoal material, is that human known intensity is the highest, and electroconductibility, the best material of thermal conductivity are matrix material ideal strongtheners, and none does not competitively develop countries in the world it as critical material.The appearance of Graphene is expected to from structured material to the wide spectrum atarting material revolutions such as functional material that are used for electron device.Graphene maybe will become the core material of multiple devices of new generation such as high performance composite, high speed transistor, high sensor, laser apparatus, touch panel, ultracapacitor, store battery and high performance solar batteries.
Mainly contain physical method and chemical process about preparation method of graphene at present.Physical method is a raw material with the graphite or the expanded graphite of cheapness normally, peels off method by micromechanics and prepares the single or multiple lift Graphene, and this method raw material is easy to get, operate simple relatively, the purity height of synthetic Graphene, defective are less, but time-consuming, productive rate is low, is unsuitable for scale operation.Chemical process have usually chemical Vapor deposition process ((Chemical vapor deposition, CVD) and oxidation reduction process.Chemical Vapor deposition process is that reactive material issues biochemical reaction in quite high temperature, gaseous state condition, the solid matter that generates is deposited on the solid matrix surface of heating, and then make the Technology of solid material, the CVD method can satisfy the requirement of scale preparation high quality, big area Graphene, but present stage higher cost, complicated technology and control processing conditions accurately and restricted the development that the CVD legal system is equipped with Graphene; Oxidation reduction process is the present the most frequently used method for preparing Graphene, scientist has done a large amount of research to this respect both at home and abroad, but the employed oxygenant of this method is mainly strong oxidizers such as the vitriol oil, potassium permanganate and potassium bichromate, these reagent are difficult for reclaiming, can cause severe contamination to environment, and oxygenant has destruction to graphite linings, and there is more defective in Graphene.Therefore, exploitation is simple, high yield, high quality, large-sized preparation method of graphene are the emphasis that Graphene further develops, and also is to realize that Graphene is extensive, the low-cost precondition of using.
Summary of the invention
Purpose of the present invention provides a kind of organic solvent hydrothermal method to prepare the method for Graphene in order to overcome the shortcoming of prior art.
Purpose of the present invention can be achieved through the following technical solutions, and its principal feature is contained in following step:
1) expanded graphite or high purity graphite disperse in organic solvent under the ultrasonic wave effect, obtain the graphite dispersion liquid.
2) the graphite dispersion liquid being placed tetrafluoroethylene is the stainless steel autoclave of liner, and the High Temperature High Pressure effect obtains the Graphene dispersion liquid.
3) to the further ultra-sonic dispersion of Graphene dispersion liquid, centrifugal, collect upper strata liquid, suction filtration, the ultrasonic filter cake of water makes graphene aqueous solution, graphene aqueous solution is carried out lyophilize obtain graphene powder.
Expanded graphite described in the step 1) or high purity graphite can obtain by commercial sources.
The ultrasonic power that described in the step 1) graphite is carried out is 20-200W, and ultrasonic time is 1-300 hour.Organic solvent is selected from following at least a: tetrahydrofuran (THF), N, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), toluene.The concentration of graphite dispersion liquid is 0.1-10mg/mL.
Step 2) temperature to the graphite dispersion liquid described in is 50-220 ℃.
The ultrasonic power that described in the step 3) Graphene dispersion liquid is carried out is 20-200W, and ultrasonic time is 1-300 hour, is 500-5000rpm to Graphene dispersion liquid centrifugal rotation speed, and centrifugation time is 5-100 minute.The centrifugal purpose is to remove multilayer graphite, obtains high quality, low number of plies Graphene.
The present invention prepares Graphene in a large number, and advantage is: (1) raw materials used cost is low; (2) simple to operate, can use on a large scale; (3) solvent for use is reusable, saves cost.
The present invention has prepared Graphene by solvent-thermal method and the ultrasonic method bonded means of peeling off.Adopt scanning electronic microscope, transmission electron microscope to characterize the pattern of Graphene; Characterized the defective of Graphene with Raman spectrum.The result shows, it is big that the Graphene of the inventive method preparation has size, the quality height, and advantage such as defective is few provides the method for feasibility to the application of extensive Graphene.
Description of drawings
Fig. 1 is the exterior appearance figure of preparation Graphene.
Fig. 2 is the electron scanning micrograph of the Graphene for preparing of embodiment 1.
Fig. 3 is the transmission electron microscope photo of the Graphene for preparing of embodiment 1.
Fig. 4 is the selected area electron diffraction photo of the Graphene for preparing of embodiment 1.
Fig. 5 is the Raman spectrum of the Graphene for preparing of embodiment 1.
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be Graphene product shape appearance figure, as seen from the figure: graphene powder is bulk shape black powder.
Shown in Figure 2, be the Graphene electron scanning micrograph, can find clearly that by figure prepared graphene is a single-layer graphene, size is about 2 μ m.
Shown in Figure 3, be the transmission electron microscope photo of Graphene, by the passable pattern of observing the thin layer Graphene of figure.
Shown in Figure 4, be the selected area electron diffraction photo of Graphene, electron-diffraction diagram is the hexagon of standard as can be seen from Figure, illustrates that the prepared graphene crystallization degree is fine, defective is less.
Shown in Figure 5, be the Raman spectrogram of Graphene, Graphene has the D peak (1350cm that small pieces are formed as seen from the figure
-1), and stronger G peak (1580cm
-1) and tangible 2D peak (2700cm
-1), the 2D peak is better than the D peak, illustrates that prepared graphene is based on individual layer.
Embodiment
The present invention prepares the Graphene method and mainly comprises following a few step:
The first step: the preparation of graphite dispersion liquid
Expanded graphite or high purity graphite are joined in the organic solvent, under ultrasonication, form the graphite dispersion liquid.
Second step: the preparation of low pure Graphene dispersion liquid
The graphite dispersion liquid that makes in the first step is placed the tetrafluoroethylene autoclave, react under the High Temperature High Pressure, obtain low pure Graphene dispersion liquid.
The 3rd step: the preparation of high purity graphite alkene dispersion liquid
The low pure Graphene dispersion liquid that makes in second step is carried out ultrasonic and high speed centrifugation, collect upper strata liquid, obtain high-purity dispersion liquid.
The 4th step: the preparation of Graphene
The high purity graphite alkene dispersion liquid that the 3rd step made is removed organic solution with cellulose membrane high pressure suction filtration, obtain graphene aqueous solution with the ultrasonic Graphene of distilled water then, at last the graphene aqueous solution lyophilize is obtained Graphene.Concrete embodiment is as follows:
Embodiment 1:
The 100mg expanded graphite is joined in the 100mL tetrahydrofuran solution, under the ultrasonic power of 200W, ultrasonic 10 hours, obtain the graphite dispersion liquid; Then the graphite dispersion liquid is placed the tetrafluoroethylene autoclave of 200mL, 150 ℃ of reaction 24h are cooled to room temperature and obtain low pure Graphene dispersion liquid; To hang down pure Graphene dispersion liquid and place the 150mL beaker,, obtain a large amount of dark solution with the power ultrasonic of 200W 5 hours; Dark solution is joined in the plastic centrifuge tube of 30mL, with 500 rev/mins rotating speed, centrifugal 30 minutes, draw supernatant liquid with suction pipe, obtain high purity graphite alkene solution; With high purity graphite alkene solution cellulose membrane suction filtration, use 100mL distilled water at last, under the ultrasonic power of 200W ultrasonic 5 hours, obtain graphene aqueous solution, under-40 ℃, the graphene aqueous solution lyophilize is obtained Graphene.
Embodiment 2:
Preparation method of graphene is substantially with embodiment 1.Difference is: when preparation graphite dispersion liquid, adopt N respectively, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), toluene.Can obtain Graphene equally.
Embodiment 3:
Preparation method of graphene is substantially with embodiment 1.Difference is: when the low pure Graphene dispersion liquid of preparation, temperature of reaction is set at 170 ℃, can obtain Graphene equally.
Embodiment 4:
Preparation method of graphene is substantially with embodiment 1.Difference is: when the low pure graphite dispersion liquid of preparation, will the reaction times be set at 48h, and can obtain Graphene equally.
Embodiment 5:
Preparation method of graphene is substantially with embodiment 1.Difference is: when preparation graphite dispersion liquid, the 300mg high purity graphite is joined in the 100mL tetrahydrofuran solution, can obtain Graphene equally.
Embodiment 6:
Preparation method of graphene is substantially with embodiment 1.Difference is: when preparation high purity graphite dispersion liquid, centrifugal rotational speed is adjusted to 1500 rev/mins, can obtains Graphene equally.
Embodiment 7:
Preparation method of graphene is substantially with embodiment 1.Difference is: when preparation high purity graphite dispersion liquid, ultrasonic power is set at 50W, can obtains Graphene equally.
Claims (7)
1. a solvent-thermal method prepares the method for Graphene, comprises the steps:
1) expanded graphite or high purity graphite disperse in organic solvent under ultrasonication, obtain the graphite dispersion liquid.
2) the graphite dispersion liquid is placed the tetrafluoroethylene autoclave, the High Temperature High Pressure effect makes the Graphene dispersion liquid.
3) to the further ultra-sonic dispersion of Graphene dispersion liquid, centrifugal, collect upper strata liquid, suction filtration, the ultrasonic filter cake of water make graphene aqueous solution, and lyophilize obtains graphene powder to graphene aqueous solution.
2. method according to claim 1 is characterized in that: the ultrasonic power that described in the step 1) expanded graphite or high purity graphite is carried out is 20-200W, and ultrasonic time is 1-300 hour.
3. method according to claim 1 is characterized in that: organic solvent described in the step 1) is selected from following at least a: tetrahydrofuran (THF), N, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), toluene.
4. method according to claim 1 is characterized in that: step 2) described in be 50-220 ℃ to the temperature of reaction of graphite dispersion liquid, pressure be under the solvent reaction temperature vapour pressure.
5. method according to claim 1 is characterized in that: the ultrasonic power that described in the step 3) Graphene dispersion liquid is carried out is 20-200W, and ultrasonic time is 1-300 hour.
6. method according to claim 1 is characterized in that: be 500-5000rpm to Graphene dispersion liquid centrifugal rotation speed described in the step 3), centrifugation time is 5-100 minute.
7. method according to claim 1 is characterized in that: be 1-100 hour to graphene aqueous solution cryodesiccated temperature-10 ℃～-70 ℃ for the time described in the step 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101697066A CN103213979A (en) | 2013-05-10 | 2013-05-10 | Method for preparing graphene by solvent-thermal process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101697066A CN103213979A (en) | 2013-05-10 | 2013-05-10 | Method for preparing graphene by solvent-thermal process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103213979A true CN103213979A (en) | 2013-07-24 |
Family
ID=48812210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101697066A Pending CN103213979A (en) | 2013-05-10 | 2013-05-10 | Method for preparing graphene by solvent-thermal process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103213979A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594714A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Fluorinated graphene electrode material and preparation method thereof |
| CN103723708A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of organic single-layer graphene solution |
| CN103723714A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene hexahydrotoluene solution |
| CN103723713A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene toluene solution |
| CN103723712A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene dimethylformamide solution |
| CN103738948A (en) * | 2013-11-22 | 2014-04-23 | 盐城纳新天地新材料科技有限公司 | Preparation method for single-layer graphene n-butyl alcohol solution |
| CN103738947A (en) * | 2013-11-22 | 2014-04-23 | 盐城纳新天地新材料科技有限公司 | Preparation method for single-layer graphene ethylene glycol solution |
| CN104843679A (en) * | 2015-04-03 | 2015-08-19 | 北京理工大学 | Method for solvothermal peeling preparation of microcrystalline graphene from microcrystalline graphite |
| CN105293482A (en) * | 2015-12-01 | 2016-02-03 | 张扬威 | Solvothermal stripping preparation method of graphene |
| CN105439126A (en) * | 2014-09-01 | 2016-03-30 | 华北电力大学 | Simple preparation method of millimeter level monocrystalline graphene |
| CN105936505A (en) * | 2016-06-23 | 2016-09-14 | 南京先丰纳米材料科技有限公司 | Preparation method of single layer graphene |
| CN108751792A (en) * | 2018-05-12 | 2018-11-06 | 深圳莱必德科技股份有限公司 | A kind of graphene heat dissipation plastic particles manufacturing method |
| CN110157068A (en) * | 2018-03-27 | 2019-08-23 | 北京欧美中科学技术研究院 | A kind of ultra-high molecular weight polyethylene special graphite alkene microballoon mother material and preparation method |
| CN114735685A (en) * | 2022-04-21 | 2022-07-12 | 武汉理工大学 | Preparation method of fluorinated graphene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671015A (en) * | 2009-10-13 | 2010-03-17 | 南昌航空大学 | Method of producing graphene |
| CN101746754A (en) * | 2009-10-13 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing grapheme through organic amine solvothermal method |
| KR20110121584A (en) * | 2010-04-30 | 2011-11-07 | 연세대학교 산학협력단 | Transition metal oxide/graphene composites by using microwave-water process and synthesizing method thereof |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102730668A (en) * | 2011-04-07 | 2012-10-17 | 东丽纤维研究所（中国）有限公司 | Method for preparing grapheme through solvothermal technique based on aromatic alcohol |
-
2013
- 2013-05-10 CN CN2013101697066A patent/CN103213979A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671015A (en) * | 2009-10-13 | 2010-03-17 | 南昌航空大学 | Method of producing graphene |
| CN101746754A (en) * | 2009-10-13 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing grapheme through organic amine solvothermal method |
| KR20110121584A (en) * | 2010-04-30 | 2011-11-07 | 연세대학교 산학협력단 | Transition metal oxide/graphene composites by using microwave-water process and synthesizing method thereof |
| CN102730668A (en) * | 2011-04-07 | 2012-10-17 | 东丽纤维研究所（中国）有限公司 | Method for preparing grapheme through solvothermal technique based on aromatic alcohol |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
Non-Patent Citations (1)
| Title |
|---|
| 陈敬中等: "《现代晶体化学》", 31 May 2010, 科学出版社 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594714A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Fluorinated graphene electrode material and preparation method thereof |
| CN103738947A (en) * | 2013-11-22 | 2014-04-23 | 盐城纳新天地新材料科技有限公司 | Preparation method for single-layer graphene ethylene glycol solution |
| CN103723714A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene hexahydrotoluene solution |
| CN103723713A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene toluene solution |
| CN103723712A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of single-layer graphene dimethylformamide solution |
| CN103738948A (en) * | 2013-11-22 | 2014-04-23 | 盐城纳新天地新材料科技有限公司 | Preparation method for single-layer graphene n-butyl alcohol solution |
| CN103723708A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of organic single-layer graphene solution |
| CN105439126B (en) * | 2014-09-01 | 2017-12-22 | 华北电力大学 | A kind of grade single crystal graphene preparation method |
| CN105439126A (en) * | 2014-09-01 | 2016-03-30 | 华北电力大学 | Simple preparation method of millimeter level monocrystalline graphene |
| CN104843679A (en) * | 2015-04-03 | 2015-08-19 | 北京理工大学 | Method for solvothermal peeling preparation of microcrystalline graphene from microcrystalline graphite |
| CN105293482A (en) * | 2015-12-01 | 2016-02-03 | 张扬威 | Solvothermal stripping preparation method of graphene |
| CN105936505A (en) * | 2016-06-23 | 2016-09-14 | 南京先丰纳米材料科技有限公司 | Preparation method of single layer graphene |
| CN110157068A (en) * | 2018-03-27 | 2019-08-23 | 北京欧美中科学技术研究院 | A kind of ultra-high molecular weight polyethylene special graphite alkene microballoon mother material and preparation method |
| CN108751792A (en) * | 2018-05-12 | 2018-11-06 | 深圳莱必德科技股份有限公司 | A kind of graphene heat dissipation plastic particles manufacturing method |
| CN114735685A (en) * | 2022-04-21 | 2022-07-12 | 武汉理工大学 | Preparation method of fluorinated graphene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103213979A (en) | Method for preparing graphene by solvent-thermal process | |
| CN101746755B (en) | Method for preparing multi-layer graphene | |
| US9249026B2 (en) | Method for preparing graphene from biomass-derived carbonaceous mesophase | |
| CN101513998B (en) | Method for preparing ordered graphene oxide films | |
| CN101746754B (en) | Method for preparing grapheme through organic amine solvothermal method | |
| CN104891479B (en) | Plant-based graphene and preparation method thereof | |
| CN102583338B (en) | High-quality graphene powder and preparation method thereof | |
| CN102491314A (en) | Method for preparing graphene | |
| CN102807210B (en) | Method for preparing graphene by biomass derived carbonaceous mesophase | |
| CN103922330A (en) | Method for preparing graphene powder by using dry process | |
| CN104211058A (en) | Method for preparing graphene from conducting polymer polyaniline | |
| CN102765712A (en) | Method for preparing carbon microspheres | |
| CN102464312B (en) | Preparation method of graphene | |
| CN103922331A (en) | Method of preparing graphene powder | |
| CN107140623B (en) | A method of preparing graphene | |
| CN103626162A (en) | Preparation method of graphene | |
| CN105016331B (en) | Synthetic method of graphene microchip-diamond compound | |
| Kamel et al. | Graphene’s Structure, Synthesis, and Characterization; a brief review | |
| CN106477568A (en) | A kind of method preparing Graphene using liquid nitrogen gas phase stripping | |
| Sharma et al. | Synthesis of silica and carbon-based nanomaterials from rice husk ash by ambient fiery and furnace sweltering using a chemical method | |
| CN103420362A (en) | Preparation method for graphene | |
| CN107720825B (en) | A kind of method that simple intercalation stripping obtains molybdenum disulfide nano sheet | |
| CN109250707B (en) | Graphene material prepared from waste tires and preparation method thereof | |
| CN108059147A (en) | A kind of method for preparing carbon material using discarded sunflower | |
| CN111410230A (en) | Graphene/molybdenum disulfide composite material and liquid phase preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130724 |
|
| RJ01 | Rejection of invention patent application after publication |