CN103922331A - Method of preparing graphene powder - Google Patents
Method of preparing graphene powder Download PDFInfo
- Publication number
- CN103922331A CN103922331A CN201410173741.XA CN201410173741A CN103922331A CN 103922331 A CN103922331 A CN 103922331A CN 201410173741 A CN201410173741 A CN 201410173741A CN 103922331 A CN103922331 A CN 103922331A
- Authority
- CN
- China
- Prior art keywords
- graphene powder
- preparing graphene
- graphite
- graphene
- reduction
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the technical field of preparation of nano materials and particularly relates to a method of preparing high-quality graphene powder in a large scale. According to the technical scheme, the method comprises the following steps: first, adding an intercalator to graphite to form a graphite intercalated compound; then, placing the graphite intercalated compound in a high pressure-resistant peeling reactor, and adding a swelling agent for high-pressure and high-speed peeling to obtain graphene containing radicals; and reducing the graphene to obtain the graphene powder. The method of preparing graphene powder provided by the invention has the advantages of simple production equipment, few process flows, environment protection and suitability for mass production. The prepared graphene powder hardly has defects, has good conductivity and is suitable for the application field such as supercapacitors, sensors and sea water desalination.
Description
Technical field
The invention belongs to the preparing technical field of nano material, be specifically related to a kind of method of preparing graphene powder.
Background technology
Found that from 2004 many scientists are devoted to the research of graphene preparation method since Graphene, especially to prepare high quality, productive rate is high, cost is low, the method for constitutionally stable Graphene this just seem particularly important.The method of preparing at present Graphene mainly contains following several: stripping method, comprises the method such as micromechanics stripping method and solvent stripping method; Growth method, comprises that crystal is to methods such as epitaxy, epitaxy method, chemical vapour depositions; Redox graphite method, comprises conventional Hummers method, Standenmaier method, Brodie method etc.; In addition, also have arc discharge method, graphite layers chemicals approach method, carbon nanotube strip off method etc.Redox graphite method has the technique of simple and diversification, be a kind of conventional method of preparing Graphene, still, this method is only applicable to laboratory on a small quantity for the preparation of research, and a large amount of preparations easily produce a large amount of spent acid, waste water etc., will cause the pollution of environment.Therefore, a kind of technique of urgent need development is simple, environmental pollution is little, the graphene preparation method of easy large-scale production.
Summary of the invention
Based on the problem of prior art, the object of the present invention is to provide a kind of method of preparing on a large scale graphene powder, its technical scheme comprises the following steps:
(1) graphite is added in the solution of intercalator, uniform stirring, obtains graphite intercalation compound;
(2) graphite intercalation compound is placed in high pressure resistant stripping reaction device, and adds swelling agent to carry out high-voltage high-speed to peel off, obtain the Graphene that contains group;
(3) Graphene that contains group is reduced to processing, washing and drying afterwards, obtains graphene powder.
Wherein, in step (1), the mass ratio of graphite and intercalator is 1:20 ~ 100:1, preferably 10:1 ~ 30:1, intercalator is any one or the two or more mixture in formic acid, acetic acid, ethanol, propyl alcohol, methylamine, ethamine, quadrol, the concentration of intercalator is 1 ~ 120g/L.
Wherein, in step (2), high pressure resistant stripping reaction device is any one in high speed ball mill, high-speed stirring reactor, pair roller mill; The rotating speed of described high pressure resistant stripping reaction device is 600-6000 rev/min, and the time of ball milling or stirring is 2 ~ 72h.
Wherein, in step (2), swelling agent is dry ice, liquid nitrogen, liquid oxygen, supercritical CO
2in any one or multiple mixture, the mass ratio of swelling agent and graphite is 1:50 ~ 100:1, preferential 5:1-30:1; Add swelling agent mainly to utilize volumetric expansion in its gasification or liquefaction process, discharge high pressure, urge the expansion into graphite intercalation compound, and then more effective peeling off.
Wherein, in step (3), reduction is treated to high temperature reduction or laser reduction, and high temperature reduction condition is: under pure nitrogen gas condition, reduction temperature is 300-900 DEG C, and the reaction times is 0.5-24 h hour; The condition of laser reduction is: the wavelength region of pulse laser is 150-400 nm, and frequency is greater than 2Hz, and the burst length is 1s-60 min.
Technique effect of the present invention and advantage: the graphene powder defect of preparation is few, good conductivity, and production unit is simple, technical process is few, is applicable to scale operation.
Brief description of the drawings
Fig. 1 is graphene powder preparation process schema.
Fig. 2 is the Raman collection of illustrative plates that embodiment 1 is prepared into graphene powder.
Fig. 3 is transmission electron microscope (TEM) figure that embodiment 2 prepares graphene powder.
Fig. 4 is atomic force microscope (AFM) figure that embodiment 2 prepares graphene powder.
Embodiment
The schema that the inventive method is prepared graphene powder process as shown in Figure 1, below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in detail, but the explanation of described embodiment, is only a part of embodiment of the present invention, and wherein major part is not limited in this.
Embodiment 1
(1) taking 20g expansible black lead, to add concentration be in the ethanolic soln of 200ml of 10g/L, stirred, and obtains graphite intercalation alcohol cpd;
(2) the graphite intercalation alcohol cpd of step (1) being placed in high-voltage ball miller (ball grinder volume is 2L), and adding 80g dry ice, is under 2000 revs/min of conditions at rotating speed, peels off 24 hours, obtains the Graphene containing group;
(3) Graphene containing group in step (2) is placed in to high temperature process furnances, at 600 DEG C and N
2under atmospheric condition, reduce 4 hours, obtain Graphene, used deionized water wash 5 times, and be put in 80 DEG C of baking ovens and dry, obtain graphene powder.
The Graphene sample of preparation is carried out to Raman Characterization, and as shown in Figure 2, as seen from the figure, D peak position is in 1361.94 for its result
-1, G peak position is in 1605.93cm
-1place, illustrates and utilizes this technical scheme can generate Graphene.
embodiment 2
(1) taking 15g expansible black lead, to add concentration be in the acetic acid solution of 180ml of 80g/L, stirred, and obtains graphite intercalation acetic acid compound;
(2) the graphite intercalation acetic acid compound of step (1) being placed in to high-speed stirring reactor, and adding 60g liquid nitrogen, is under 18000 revs/min of conditions at rotating speed, peels off 24 hours, obtains the Graphene containing group;
(3) in the pulse laser direct irradiation step (2) that is 248nm with wavelength, containing the graphene solution 2min of group, reduction obtains Graphene, by Graphene washing with alcohol 3 times, and is put in 80 DEG C of drying in oven, obtains graphene powder.
The Graphene sample of preparation is carried out to TEM and AFM sign, and respectively as shown in Figure 3 and Figure 4, as seen from the figure, the Graphene of preparation is transparent tulle shape structure to its result, and surface is accordion.
Claims (8)
1. a method of preparing graphene powder, comprises the following steps:
(1) graphite is added in the solution of intercalator, uniform stirring, obtains graphite intercalation compound;
(2) graphite intercalation compound is placed in high pressure resistant stripping reaction device, and adds swelling agent to carry out high-voltage high-speed to peel off, obtain the Graphene that contains group;
(3) Graphene that contains group is reduced to processing, wash afterwards, dry, obtain graphene powder.
2. a kind of method of preparing graphene powder according to claim 1, is characterized in that: in step (1), the mass ratio of graphite and intercalator is 1:20 ~ 100:1, preferably 10:1 ~ 30:1.
3. a kind of method of preparing graphene powder according to claim 1, is characterized in that: described intercalator is any one or the two or more mixture in formic acid, acetic acid, ethanol, propyl alcohol, methylamine, ethamine, quadrol; The concentration of described intercalator is 1 ~ 120g/L.
4. a kind of method of preparing graphene powder according to claim 1, is characterized in that: described high pressure resistant stripping reaction device is any one in high speed ball mill, high-speed stirring reactor, pair roller mill; The rotating speed of described high pressure resistant stripping reaction device is 600-6000 rev/min, and the time of ball milling or stirring is 2 ~ 72h.
5. a kind of method of preparing graphene powder according to claim 1, is characterized in that: described swelling agent is dry ice, liquid nitrogen, liquid oxygen, supercritical CO
2in any one or multiple mixture, the mass ratio of swelling agent and graphite is 1:50 ~ 100:1, preferential 5:1-30:1.
6. a kind of method of preparing graphene powder according to claim 1, is characterized in that: described reduction is treated to high temperature reduction or laser reduction.
7. according to a kind of method of preparing graphene powder described in claim 1 or 6, it is characterized in that: the condition of described high temperature reduction is: under pure nitrogen gas condition, reduction temperature is 300-900 DEG C, and the reaction times is 0.5-24 h.
8. according to a kind of method of preparing graphene powder described in claim 1 or 6, it is characterized in that: the condition of described laser reduction is: the wavelength region of pulse laser is 150-400 nm, and frequency is greater than 2Hz, the burst length is 1s-60 min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410173741.XA CN103922331A (en) | 2014-04-28 | 2014-04-28 | Method of preparing graphene powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410173741.XA CN103922331A (en) | 2014-04-28 | 2014-04-28 | Method of preparing graphene powder |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103922331A true CN103922331A (en) | 2014-07-16 |
Family
ID=51140767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410173741.XA Pending CN103922331A (en) | 2014-04-28 | 2014-04-28 | Method of preparing graphene powder |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103922331A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105197916A (en) * | 2014-06-09 | 2015-12-30 | 余泉茂 | Novel method for preparing graphene/oxidized graphene |
CN105293482A (en) * | 2015-12-01 | 2016-02-03 | 张扬威 | Solvothermal stripping preparation method of graphene |
CN105540574A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene micro-sheets by using counter-jet jet mill |
CN106082195A (en) * | 2016-06-17 | 2016-11-09 | 青岛大学 | A kind of ball milling formula preparation method of Graphene |
CN106185886A (en) * | 2016-07-01 | 2016-12-07 | 成都新柯力化工科技有限公司 | The method of Graphene and prepared Graphene powder are prepared in a kind of continuous scale |
CN106672950A (en) * | 2016-12-06 | 2017-05-17 | 北京化工大学 | Preparation method of organic modified graphene |
CN108622886A (en) * | 2017-03-17 | 2018-10-09 | 国家纳米科学中心 | A kind of liquid nitrogen auxiliary prepares the method for high-quality graphene and high-quality graphene obtained |
CN109666350A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene |
CN111422857A (en) * | 2020-01-14 | 2020-07-17 | 昂星新型碳材料常州有限公司 | Graphene nano-bubble material, preparation method and application thereof, adsorbent, catalyst, optical material and energy storage material |
CN112441579A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
-
2014
- 2014-04-28 CN CN201410173741.XA patent/CN103922331A/en active Pending
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105197916A (en) * | 2014-06-09 | 2015-12-30 | 余泉茂 | Novel method for preparing graphene/oxidized graphene |
CN105293482A (en) * | 2015-12-01 | 2016-02-03 | 张扬威 | Solvothermal stripping preparation method of graphene |
CN105540574A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene micro-sheets by using counter-jet jet mill |
CN106082195A (en) * | 2016-06-17 | 2016-11-09 | 青岛大学 | A kind of ball milling formula preparation method of Graphene |
CN106185886A (en) * | 2016-07-01 | 2016-12-07 | 成都新柯力化工科技有限公司 | The method of Graphene and prepared Graphene powder are prepared in a kind of continuous scale |
CN106672950B (en) * | 2016-12-06 | 2018-12-04 | 北京化工大学 | A kind of preparation method of organic modification graphene |
CN106672950A (en) * | 2016-12-06 | 2017-05-17 | 北京化工大学 | Preparation method of organic modified graphene |
CN108622886A (en) * | 2017-03-17 | 2018-10-09 | 国家纳米科学中心 | A kind of liquid nitrogen auxiliary prepares the method for high-quality graphene and high-quality graphene obtained |
CN109666350A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene |
CN109666350B (en) * | 2017-10-16 | 2021-06-29 | 山东欧铂新材料有限公司 | Water-based conductive coating containing high-conductivity graphene and preparation method thereof |
CN112441579A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
CN112441579B (en) * | 2019-08-30 | 2022-11-15 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
CN111422857A (en) * | 2020-01-14 | 2020-07-17 | 昂星新型碳材料常州有限公司 | Graphene nano-bubble material, preparation method and application thereof, adsorbent, catalyst, optical material and energy storage material |
CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103922331A (en) | Method of preparing graphene powder | |
CN103922330A (en) | Method for preparing graphene powder by using dry process | |
CA2999904C (en) | Industrial method for preparing large-sized graphene | |
CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
Zhang et al. | A novel route for preparation of high-performance porous carbons from hydrochars by KOH activation | |
CN106517171B (en) | A kind of preparation method of graphene aerogel | |
CN108002374A (en) | A kind of ultra-thin two-dimension stratified material nanometer sheet and preparation method thereof | |
CN102583332B (en) | Technology and method for preparing solution used for preparing graphene in liquid phase | |
CN104891479B (en) | Plant-based graphene and preparation method thereof | |
CN108529679B (en) | Method for preparing molybdenum disulfide nanosheet through polyol stripping | |
CN108163847B (en) | Preparation method of large-sheet-diameter graphene and large-sheet-diameter graphene | |
CN103253659A (en) | Method for preparing graphene through carrying out ultrasonic stripping on graphite | |
CN102910624A (en) | Preparation method of high-yield graphene without defects | |
CN103482607A (en) | Enrichment method of semiconductor type carbon nanotubes | |
CN106865529A (en) | A kind of preparation method of the microwave radiation technology high-quality redox graphene of triggering mode | |
CN104692363A (en) | Method for preparing graphene through hypergravity technology | |
Guo et al. | Preparation of graphene via liquid-phase exfoliation with high gravity technology from edge-oxidized graphite | |
CN102583326B (en) | Method for preparing graphite by compressing CO2 fluid under ultrasonic assistance | |
CN107402247A (en) | A kind of preparation method of electrochemical sensor nano-graphene/chitosan complex film modified electrode | |
Shen et al. | Preparation of high quality graphene using high gravity technology | |
CN102698741B (en) | Method for preparing grapheme platinum nanocomposite material by using argon plasma | |
CN104477995B (en) | A kind of MoO2the preparation method of nanometer sheet and MoO2nanometer sheet | |
CN104528737B (en) | Preparation method of a kind of nano level stratiform silicon-dioxide/graphene composite material and products thereof | |
CN103922325B (en) | A kind of preparation method of Graphene | |
CN103418159A (en) | New method for preventing nano particles from re-agglomerating during rapid expansion of supercritical fluid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140716 |
|
WD01 | Invention patent application deemed withdrawn after publication |