CN104071774A - Method for preparing fluorinated graphene - Google Patents
Method for preparing fluorinated graphene Download PDFInfo
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- CN104071774A CN104071774A CN201310109510.8A CN201310109510A CN104071774A CN 104071774 A CN104071774 A CN 104071774A CN 201310109510 A CN201310109510 A CN 201310109510A CN 104071774 A CN104071774 A CN 104071774A
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Abstract
The invention discloses a method for preparing fluorinated graphene. The method adopts an arc discharge method to prepare large-size fluorinated graphene. The fluorinated graphene prepared by using the method has the characteristics of regular graphitic layer, good crystal form, small amount of defects, high purity, high yield and the like, moreover the equipment is simple, the preparation period is shorter than that of a chemical method, large-scale preparation can be achieved, the size of the fluorinated graphene is large (greater than 1 [mu m]), and the product purity is high.
Description
Technical field
The present invention relates to a kind of preparation method of fluorinated graphene.
Background technology
Fluorinated graphene is a kind of brand-new carbon nanomaterial, and bibliographical information is little at present.It has concentrated Graphene and fluorographite feature performance benefit, and the introducing of fluorine element is expected to be applied in more field.Fluorinated graphene is to have high strength and high Young's modulus, good chemical property, thermostability and insulativity, the features such as excellent abrasion resistance.Wherein, because fluorinated graphene surface is the overlay structure of chemical bond (→ F) composition, the surface little interlamellar spacing of energy is large, under various severe condition (as high temperature, high pressure and high-load), all shows good lubricity, can be as solid lubricant.The U.S., Japan studies have shown that, fluorographite is applicable to doing high tension battery anode material, and fluorine content height is conducive to reduce anode volume, makes battery miniaturization.Because fluorinated graphene has broad-band gap, there is essential difference in electricity and optical property with the derivative of other Graphenes as graphene oxide and hydrogenation Graphene, its light transmission increases; Aspect electronics, the metallicity complementation of the insulativity of this material and fertile material, can be used for atomic thickness isolator or tunnel junction.
The main method of preparing at present fluorinated graphene has Graphene to fluoridize with micromechanics to peel off these two kinds of fluorographites.Front a kind of be that the Graphene preparing is passed into F in the closed environment of strict controlling moisture and pressure
2or XeF
2realize, due to this method reaction environment and equipment requirements are all got well high, reaction be difficult for and danger larger, be restively difficult to realize industrialization; And the fluorinated graphene of the Graphene character that second method prepares and partial reduction is similar, wants to obtain the less controlled fluorinated graphene of the number of plies and in technique, be difficult to realize.In fluorinated graphene preparation and aspect of performance research few, the potential application in a lot of fields of fluorinated graphene becomes one of focus of research at present, but technology of preparing is as the basis of research, and finding easy, economical, effective preparation method is key.
In more than ten years in the past, sharp arc discharge method has been prepared soccerballene, carbon nanotube, nano-tube, the nano materials such as metal nano powder.Recent years, utilize arc-discharge technique successfully to prepare again this New Two Dimensional carbon nanomaterial of Graphene
Summary of the invention
The object of the present invention is to provide a kind of method of preparing fluorinated graphene simple and easy to operate, the fluorinated graphene of preparing by the method has that purity is high, size is large, the less feature such as controlled of the number of plies.
The present invention utilizes arc discharge method to prepare large size fluorinated graphene, the fluorinated graphene that this method is prepared has the features such as graphite linings rule, crystal formation is good, defect is few, purity is high, productive rate is large, and device simple, preparation cycle is short with the cycle compared with chemical method, is expected to realize large-scale preparation.
A preparation method for fluorinated graphene, is characterized in that the preparation of fluorinated graphene is used arc discharging device, fluorographite is packed in the graphite rod of boring, compacting, in discharging chamber, pass into hydrogen and helium, carry out arc-over, after discharge off, wait cavity cooling rear collection sample completely;
The preparation method of large size fluorinated graphene carries out according to the following step:
A. electrode materials: first by high purity graphite rod boring, then fluorographite powder is packed in hole and compacting as anode combination electrode material, cathode electrode material is also high purity graphite rod.
B. gas: after cavity is evacuated to below 10Pa, then pass into the mixed gas of hydrogen and helium.
C. arc-over: the cooling system of fetching boiling water, open the device of arc preheated one-section time; Check the distance between cavity resistance to air loss and graphite rod electrode, determine errorless rear striking; Regulate electric current to 120～200A, regulating cathode rod to keep distance between cathode bar and anode bar is 1～2mm.
D. sample collection: after completion of the reaction, after waiting cavity to cool down completely, collection is deposited on cavity inner wall around and the cigarette ash at top is fluorinated graphene.
The present invention is 6～12mm at diameter, is about in the graphite rod of 100mm and holes, and aperture is 4～8mm, hole depth 50～70mm, then by fluorographite powder load hole, compacting is as anode electrode material, and cathode electrode material is that diameter is the high purity graphite rod that 12～16mm is about 100mm.
The present invention is extracted into vacuum tightness in cavity below 0.01kPa, and the volume ratio that passes into total pressure and be the mixed gas of 13.3～80.0kPa hydrogen and helium is 1:1.
More than device of arc is opened rear preheating 5min by the present invention; Discharging current is adjusted to 120～200A, and in discharge process, regulating the distance between negative electrode graphite rod and anode bar is 1～2mm.
After the present invention's electric discharge finishes, while collecting sample, only collect the cigarette ash that is deposited on cavity top and periphery of inner wall.
Preparation method of the present invention compares with the micromechanics stripping method of report and the method for fluoridizing, and equipment and process process is simple, and experiment controllability is good, and preparation cost is low, and the cycle is short, and preparation amount is large.Gained fluorinated graphene size is large, and (m), product purity is high for > 1 μ, for the more deep research of fluorinated graphene provides good preparation basis.
Fluorinated graphene prepared by this invention is launched the Modern Analytical Instrument tests such as surface sweeping Electronic Speculum (FE-SEM), transmission electron microscope (TEM) and photoelectron spectrograph (XPS) tester and is shown by field, compared with the Graphene of preparing with arc-over, fluorinated graphene has larger size, is 0.5-10 μ m.
Brief description of the drawings
Fig. 1 is fluorinated graphene (a and b) and Graphene (c and FESEM d) and TEM picture.
Embodiment
Embodiment 1:
Getting the high purity graphite rod that a long 100mm diameter is 8mm (purity 99.99%), to drill through aperture be that 4mm is the hole of 50mm deeply, take 2g fluorographite and put in hole and with graphite rod its compacting, the graphite rod of making is as anode combination electrode material.Cathode electrode material is that diameter is 12mm, is about the high purity graphite rod of 100mm.Cavity is evacuated to after 0.01kPa, is successively filled with 13.3kPa helium and 13.3kPa hydrogen.Open water cooling system and device of arc preheating 5min, check whether cavity resistance to air loss regulating YIN and YANG graphite rod electrode aligns, striking after all are normal, and discharging current being adjusted to 140A and regulating the distance between anode and cathode graphite rod is 2mm.Continuous discharge 3min.Electric discharge finishes rear cooling 30min, and logical atmosphere is collected sample, and the cigarette ash that collection is deposited on cavity finally obtains fluorinated graphene sample.
Embodiment 2:
Getting the high purity graphite rod that a long 100mm diameter is 10mm (purity 99.99%), to drill through aperture be that 6mm is the hole of 60mm deeply, take 3.5g left and right fluorographite and put in hole and with graphite rod its compacting, the graphite rod of making is as anode combination electrode material.Cathode electrode material is that diameter is 14mm, is about the high purity graphite rod of 100mm.Cavity is evacuated to 0.01kPa, is first filled with 26.6kPa helium, then be filled with 26.6kPa hydrogen turn off intake valve keep inflated condition.Open water cooling system and device of arc preheating 5min, check whether cavity resistance to air loss regulating YIN and YANG graphite rod electrode aligns, striking after all are normal, and discharging current being adjusted to 180～200A and regulating the distance between anode and cathode graphite rod is 2mm.Continuous discharge 3min.Electric discharge finishes rear cooling 30min, and logical atmosphere is collected sample, and the cigarette ash that first collection is deposited on cavity finally obtains fluorinated graphene sample.
Embodiment 3:
Getting the high purity graphite rod that a long 100mm diameter is 10mm (purity 99.99%), to drill through aperture be that 6mm is the hole of 65mm deeply, take 4g left and right fluorographite and put in hole and with graphite rod its compacting, the graphite rod of making is as anode combination electrode material.Cathode electrode material is that diameter is 14mm, is about the high purity graphite rod of 100mm.Cavity is evacuated to 0.01kPa, is first filled with 6.7kPa helium, then be filled with 6.7kPa hydrogen turn off intake valve keep inflated condition.Open water cooling system and device of arc preheating 5min, check whether cavity resistance to air loss regulating YIN and YANG graphite rod electrode aligns, striking after all are normal, and discharging current being adjusted to 200～220A and regulating the distance between anode and cathode graphite rod is 2mm.Continuous discharge 4min.Electric discharge finishes rear cooling 30min, and logical atmosphere is collected the cigarette ash that is deposited on cavity.
According to embodiment 2, utilize fluorinated graphene prepared by arc discharge method by FE-SEM and TEM, XPS test shows that the number of plies of fluorinated graphene is 5～8 layers, size is 1～5 μ m, compared with the Graphene of preparing with the method, size is larger, has further proved the formation of fluorinated graphene; Test and learn that F constituent content is 10at.% by XPS.
Claims (4)
1. the preparation method of a fluorinated graphene, the preparation that it is characterized in that fluorinated graphene is used arc discharging device, fluorographite is packed in the graphite rod of boring, compacting, in discharging chamber, pass into hydrogen and helium, carry out arc-over, after discharge off, wait cavity cooling rear collection sample completely;
The preparation method of large size fluorinated graphene carries out according to the following step:
A. electrode materials: first by high purity graphite rod boring, then fluorographite powder is packed in hole and compacting as anode combination electrode material, cathode electrode material is also high purity graphite rod;
B. gas: after cavity is evacuated to below 10Pa, then pass into the mixed gas of hydrogen and helium;
C. arc-over: the cooling system of fetching boiling water, open the device of arc preheated one-section time; Check the distance between cavity resistance to air loss and graphite rod electrode, determine errorless rear striking; Regulate electric current to 120～200A, regulating cathode rod to keep distance between cathode bar and anode bar is 1～2mm;
D. sample collection: after completion of the reaction, after waiting cavity to cool down completely, collection is deposited on cavity inner wall around and the cigarette ash at top is fluorinated graphene.
2. the method for claim 1, it is characterized in that at diameter be 6～12mm, be about in the graphite rod of 100mm and hole, aperture is 4～8mm, hole depth 50～70mm, then by fluorographite powder load hole, compacting is as anode electrode material, and cathode electrode material is that diameter is the high purity graphite rod that 12～16mm is about 100mm.
3. the method for claim 1, is characterized in that vacuum tightness in cavity to be extracted into below 0.01kPa, and the volume ratio that passes into total pressure and be the mixed gas of 13.3～80.0kPa hydrogen and helium is 1:1.
4. the method for claim 1, more than is characterized in that device of arc is opened to rear preheating 5min.
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| CN201310109510.8A CN104071774A (en) | 2013-03-29 | 2013-03-29 | Method for preparing fluorinated graphene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217613A (en) * | 2015-10-15 | 2016-01-06 | 田野 | A kind of preparation method of Graphene dopant material and application |
| CN106206056A (en) * | 2016-07-29 | 2016-12-07 | 武汉理工大学 | A kind of cobalt aluminum hydrotalcite/fluorinated graphene composite and preparation method thereof |
| CN112723349A (en) * | 2020-12-24 | 2021-04-30 | 广东工业大学 | Mild discharge preparation method and device for fluorinated graphene |
| CN114408906A (en) * | 2022-03-15 | 2022-04-29 | 枣庄市三兴高新材料有限公司 | Method for purifying coal-based graphite and simultaneously preparing fluorinated graphene |
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| JP2007084364A (en) * | 2005-09-21 | 2007-04-05 | Japan Atomic Energy Agency | Method for producing inclusion carbon nanocapsule precursor and method for producing inclusion carbon nanocapsule using the precursor |
| JP4061417B2 (en) * | 1995-12-08 | 2008-03-19 | 二郎 近藤 | Method for producing graphite and lithium secondary battery |
| CN101717083A (en) * | 2009-12-29 | 2010-06-02 | 北京大学 | Graphene and preparation method thereof |
| CN102153076A (en) * | 2011-05-04 | 2011-08-17 | 上海大学 | Method for preparing graphene with high crystallinity |
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2013
- 2013-03-29 CN CN201310109510.8A patent/CN104071774A/en active Pending
Patent Citations (4)
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| JP4061417B2 (en) * | 1995-12-08 | 2008-03-19 | 二郎 近藤 | Method for producing graphite and lithium secondary battery |
| JP2007084364A (en) * | 2005-09-21 | 2007-04-05 | Japan Atomic Energy Agency | Method for producing inclusion carbon nanocapsule precursor and method for producing inclusion carbon nanocapsule using the precursor |
| CN101717083A (en) * | 2009-12-29 | 2010-06-02 | 北京大学 | Graphene and preparation method thereof |
| CN102153076A (en) * | 2011-05-04 | 2011-08-17 | 上海大学 | Method for preparing graphene with high crystallinity |
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| BAOSHOU SHEN ET AL.: "Synthesis of fluorine-doped multi-layered graphene sheets by arc-discharge", 《RSC ADVANCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217613A (en) * | 2015-10-15 | 2016-01-06 | 田野 | A kind of preparation method of Graphene dopant material and application |
| CN106206056A (en) * | 2016-07-29 | 2016-12-07 | 武汉理工大学 | A kind of cobalt aluminum hydrotalcite/fluorinated graphene composite and preparation method thereof |
| CN112723349A (en) * | 2020-12-24 | 2021-04-30 | 广东工业大学 | Mild discharge preparation method and device for fluorinated graphene |
| CN112723349B (en) * | 2020-12-24 | 2021-08-31 | 广东工业大学 | Mild discharge preparation method and device for fluorinated graphene |
| CN114408906A (en) * | 2022-03-15 | 2022-04-29 | 枣庄市三兴高新材料有限公司 | Method for purifying coal-based graphite and simultaneously preparing fluorinated graphene |
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Application publication date: 20141001 |