CN103922331A - Method of preparing graphene powder - Google Patents

Method of preparing graphene powder Download PDF

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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
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CN
China
Prior art keywords
graphene powder
preparing graphene
graphite
graphene
reduction
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CN201410173741.XA
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Chinese (zh)
Inventor
闵永刚
宋建军
张乐乐
杨文斌
刘屹东
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YANCHENG ZENGCAI SCIENCE & TECHNOLOGY Co Ltd
Nanjing Xinyue Material Science & Technology Co Ltd
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YANCHENG ZENGCAI SCIENCE & TECHNOLOGY Co Ltd
Nanjing Xinyue Material Science & Technology Co Ltd
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Application filed by YANCHENG ZENGCAI SCIENCE & TECHNOLOGY Co Ltd, Nanjing Xinyue Material Science & Technology Co Ltd filed Critical YANCHENG ZENGCAI SCIENCE & TECHNOLOGY Co Ltd
Priority to CN201410173741.XA priority Critical patent/CN103922331A/en
Publication of CN103922331A publication Critical patent/CN103922331A/en
Pending legal-status Critical Current

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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements 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

A kind of method of preparing graphene powder
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.
CN201410173741.XA 2014-04-28 2014-04-28 Method of preparing graphene powder Pending CN103922331A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
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

Cited By (14)

* Cited by examiner, † Cited by third party
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

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