CN102009976A - Method for preparing graphene film - Google Patents
Method for preparing graphene film Download PDFInfo
- Publication number
- CN102009976A CN102009976A CN 201010607317 CN201010607317A CN102009976A CN 102009976 A CN102009976 A CN 102009976A CN 201010607317 CN201010607317 CN 201010607317 CN 201010607317 A CN201010607317 A CN 201010607317A CN 102009976 A CN102009976 A CN 102009976A
- Authority
- CN
- China
- Prior art keywords
- graphene film
- graphite
- liquid
- preparation
- film
- 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
Abstract
The invention discloses a method for preparing a graphene film, which comprises the following steps of: putting oxidized graphite or expandable graphite into a heating furnace, then quickly heating the graphite to the temperature of between 700 and 1,500 DEG C, maintaining the temperature for 0.5 to 30 minutes, naturally cooling to obtain flocculent graphite, directly grinding a certain amount of flocculent graphite into powder, putting the powder into a beaker filled with liquid, standing or stirring or ultrasonically treating the solution, and then standing the solution for certain time to form the graphene film on the liquid level. In the method, the graphene obtained by high-temperature reduction and oxidation of the graphite is used as a film forming raw material and has the advantages of good reduction effect and good film electrical conductivity; and meanwhile, the very thin film is obtained by using mutual effect between the graphene and the surface tension of the liquid, and has very good transparency.
Description
Technical field
The invention belongs to the rare preparing technical field of graphite, be specifically related to a kind of preparation method of graphene film.
Background technology
Along with the discovery of Graphene, its excellent electrical properties, mechanical property, thermal property and magnetic property have caused people's extensive concern.The method for preparing Graphene simultaneously also emerges in an endless stream, and mainly contains micromechanics and peels off method (Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV
Et al. Science 2004,306,666), chemical method (Stankovich S, Dikin DA,
Et al. Carbon 2007,45, and 1558) and epitaxy (Kim KS, Zhao Y,
Et al. Nature 2009,457, and 706).Graphene film has many excellent properties, just because of this many methods for preparing film occurred.Wherein epitaxial method and CVD method (Hofrichter J,
Et al. Nano Lett. 2010,10,36; Lee YB, Bae SK,
Et al. Nano Lett. 2010,10,490), can obtain the less and extraordinary film of performance of the number of plies, but its preparation condition harshness, the higher and film of cost is difficult to peel off; In addition, utilize the wetting ability of graphite oxide, can be earlier method by spin coating obtain the graphite oxide film, and then with hydrazine steam it is reduced again.The graphene film thickness of this method gained is comparatively speaking, and is still somewhat thick, simultaneously electric conductivity obviously reduce (Eda G, Fanchini G,
Et al. Nature Nanotec. 2008,3,270).
Summary of the invention
Goal of the invention:The invention provides a kind of preparation method of graphene film, the thin thin film thickness of the graphite that this method obtains, transparency height.
Technical scheme:A kind of preparation method of graphene film, graphite oxide or expansible black lead are put into process furnace, be warming up to 700 ℃ ~ 1500 ℃ then rapidly, and keep 0.5 ~ 30min, naturally cooling obtains cotton-shaped graphite, get cotton-shaped graphite directly or pulverize and put into the container that fills liquid, leave standstill or stirring or ultrasonic, leave standstill for some time then, can on liquid level, form graphene film.
Described process furnace can be retort furnace, vacuum tube furnace or rapid thermal anneler; Body of heater atmosphere is atmosphere, nitrogen, hydrogen or argon gas; Body of heater air pressure is a normal atmosphere or negative pressure.
Temperature rise rate is controlled at 1 ℃/s ~ 300 ℃/s.
The liquid that is filled is: a kind of or any several mixture in water, ethanol, methyl alcohol, acetone, ethylene glycol and the ionic liquid.
The temperature of liquid is at-10 ~ 100 ℃.
Beneficial effect:Compared with prior art, the present invention has following characteristics:
Present method utilizes the Graphene of high temperature reduction graphite oxide gained as the film forming raw material, it is good to have reduction effect, and the advantage that film conductivity is good is utilized the interaction between the surface tension of Graphene and liquid simultaneously, obtained extremely thin film, the transparency is very good.
The present invention is sprinkled upon cotton-shaped Graphene on the liquid level, utilize the mutual relationship of surface energy of liquid and Graphene surface energy, can obtain the high graphene film of extremely thin transparency, while is along with the difference of container dimensional, can also obtain the film of different size, the application that all these are characterized as Graphene provides wide space.
Description of drawings
Fig. 1 can find out that for the photo of the transmission electron microscope of the film fished for copper mesh film is transparence, and is extremely thin, also has a lot of gauffers simultaneously, and surface-area is quite big.The formation partly cause of gauffer may be after copper mesh is fished for, because due to the capillary contraction;
Fig. 2 is the transmission electron microscope photo of the bigger magnification of this film, has more further proved the thickness of film.
Embodiment
The invention will be further described below in conjunction with example:
Embodiment 1
The first step, in Erlenmeyer flask, add the 46mL vitriol oil, and place 0 ± 1 ℃ ice bath, slowly add 2g expansible black lead and 1g SODIUMNITRATE then, then divide and add 6g potassium permanganate (timed interval is 15 minutes) four times, after finishing Erlenmeyer flask is moved under the room temperature, places the stirring that 16h(does not stop), then add 92mL water and temperature is increased to 98 ℃ and keep 15min with the slow successive of syringe; Finish the back and be diluted to 280mL, and add the hydrogen peroxide of 6mL 30%wt with warm water; Next be exactly to clean while hot, at first clean 7 times to remove sulfate ion with the dilute hydrochloric acid of 5%wt, then again with washed with de-ionized water 7 times to remove chlorion and to check with Silver Nitrate; Under 60 ℃, carry out the drying of 15h at last exactly;
Second step, the exsiccant graphite oxide is placed on the quartz boat, and send in the silica tube, open the nitrogen valve, feed nitrogen 10min in the silica tube of tube furnace, then the temperature rise rate with 10 ℃/s is rapidly heated 1300 ℃, and keeps 5min, then below the fast cooling to 500 ℃, stop to feed nitrogen and naturally cooling.
The 3rd step, the cotton-shaped Graphene that obtains is spilt on the water surface in beaker, and stir gently, can form graphene film as shown in Figure 1, 2.
Embodiment 2
The preparation method is substantially with embodiment 1, and difference is, has changed graphite oxide into expanded graphite, and the Graphene after the reduction that obtains spills and can obtain being similar to result shown in Figure 1 on the water surface.
Embodiment 3
The preparation method is substantially with embodiment 1, and difference is that silica tube is not to be full of nitrogen, but is evacuated, the Graphene that obtains.
Embodiment 4
The preparation method is substantially with embodiment 1, and difference is that temperature rise rate becomes 50 ℃/s by 10 ℃/s, and the film that the Graphene that obtains forms is similar to the result shown in Fig. 1,2.
Embodiment 5
The preparation method is substantially with embodiment 4, and difference is that holding temperature becomes 1100 ℃ by 1300 ℃, obtains similar results shown in Figure 1 equally.
Embodiment 6
The preparation method is substantially with embodiment 1, and difference is that the water in the beaker has been become ionic liquid, obtains similar results shown in Figure 1 equally.
Embodiment 7
The preparation method is substantially with embodiment 6, and difference is that ionic liquid has changed organic solvent ethanol into, has obtained being similar to result shown in Figure 1.
Embodiment 8
A kind of preparation method of graphene film, graphite oxide or expansible black lead are put into process furnace, be warming up to 700 ℃ ~ 1500 ℃ then rapidly, and keep 0.5 ~ 30min, naturally cooling obtains cotton-shaped graphite, get cotton-shaped graphite directly or pulverize and put into the container that fills liquid, leave standstill or stirring or ultrasonic, leave standstill for some time then, can on liquid level, form graphene film.Described process furnace can be retort furnace, vacuum tube furnace or rapid thermal anneler; Body of heater atmosphere is atmosphere, nitrogen, hydrogen or argon gas; Body of heater air pressure is a normal atmosphere or negative pressure.Temperature rise rate is controlled at 1 ℃/s ~ 300 ℃/s.The liquid that is filled is: a kind of or any several mixture in water, ethanol, methyl alcohol, acetone, ethylene glycol and the ionic liquid.The temperature of liquid is at-10 ~ 100 ℃.
Claims (5)
1. the preparation method of a graphene film, it is characterized in that: graphite oxide or expansible black lead are put into process furnace, be warming up to 700 ℃ ~ 1500 ℃ then rapidly, and keep 0.5 ~ 30min, naturally cooling obtains cotton-shaped graphite, get cotton-shaped graphite directly or pulverize and put into the container that fills liquid, leave standstill or stirring or ultrasonic, leave standstill for some time then, can on liquid level, form graphene film.
2. according to the preparation method of the described graphene film of claim 1, it is characterized in that: described process furnace can be retort furnace, vacuum tube furnace or rapid thermal anneler; Body of heater atmosphere is atmosphere, nitrogen, hydrogen or argon gas; Body of heater air pressure is a normal atmosphere or negative pressure.
3. according to the preparation method of the described graphene film of claim 1, it is characterized in that: temperature rise rate is controlled at 1 ℃/s ~ 300 ℃/s.
4. according to the preparation method of the described graphene film of claim 1, it is characterized in that: the liquid that is filled is: a kind of or any several mixture in water, ethanol, methyl alcohol, acetone, ethylene glycol and the ionic liquid.
5. according to the preparation method of the described graphene film of claim 1, it is characterized in that: the temperature of liquid is at-10 ~ 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010607317 CN102009976A (en) | 2010-12-28 | 2010-12-28 | Method for preparing graphene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010607317 CN102009976A (en) | 2010-12-28 | 2010-12-28 | Method for preparing graphene film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102009976A true CN102009976A (en) | 2011-04-13 |
Family
ID=43840336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010607317 Pending CN102009976A (en) | 2010-12-28 | 2010-12-28 | Method for preparing graphene film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102009976A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012166001A1 (en) * | 2011-07-21 | 2012-12-06 | Общество С Ограниченной Ответственностью "Акколаб" (Ооо "Акколаб") | Process for producing graphene |
| CN103130213A (en) * | 2011-11-29 | 2013-06-05 | 施乐公司 | Graphene nano-sheets and methods for making the same |
| CN103435033A (en) * | 2013-08-12 | 2013-12-11 | 上海理工大学 | Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave |
| CN103466612A (en) * | 2013-10-08 | 2013-12-25 | 东南大学 | Method for preparing native grapheme by means of frequency mixing ultrasound |
| CN103903874A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Graphene current collector and preparing method thereof |
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN105217619A (en) * | 2015-10-23 | 2016-01-06 | 南京工业大学 | A kind of preparation method of graphene film |
| CN106672951A (en) * | 2016-12-14 | 2017-05-17 | 北京化工大学 | Environment-friendly, high-efficiency and large-scale graphene preparation method |
| CN111397231A (en) * | 2020-01-23 | 2020-07-10 | 清华大学 | Graphene-based selective absorption film system and preparation method of absorption layer thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367516A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses |
| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
-
2010
- 2010-12-28 CN CN 201010607317 patent/CN102009976A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367516A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses |
| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《J. Phys. Chem. B.》 20060411 Hannes C. Schniepp et al. Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide 8535-8539 1-5 第110卷, 第17期 2 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012166001A1 (en) * | 2011-07-21 | 2012-12-06 | Общество С Ограниченной Ответственностью "Акколаб" (Ооо "Акколаб") | Process for producing graphene |
| CN103130213A (en) * | 2011-11-29 | 2013-06-05 | 施乐公司 | Graphene nano-sheets and methods for making the same |
| CN103903874A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Graphene current collector and preparing method thereof |
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN104163417B (en) * | 2013-05-20 | 2018-01-12 | 东丽先端材料研究开发（中国）有限公司 | A kind of method for peeling off preparing graphite alkene |
| CN103435033A (en) * | 2013-08-12 | 2013-12-11 | 上海理工大学 | Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave |
| CN103435033B (en) * | 2013-08-12 | 2014-11-26 | 上海理工大学 | Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave |
| CN103466612A (en) * | 2013-10-08 | 2013-12-25 | 东南大学 | Method for preparing native grapheme by means of frequency mixing ultrasound |
| CN105217619A (en) * | 2015-10-23 | 2016-01-06 | 南京工业大学 | A kind of preparation method of graphene film |
| CN106672951A (en) * | 2016-12-14 | 2017-05-17 | 北京化工大学 | Environment-friendly, high-efficiency and large-scale graphene preparation method |
| CN106672951B (en) * | 2016-12-14 | 2019-06-11 | 北京化工大学 | A kind of environmental-friendly high efficiency can prepare with scale graphene method |
| CN111397231A (en) * | 2020-01-23 | 2020-07-10 | 清华大学 | Graphene-based selective absorption film system and preparation method of absorption layer thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102009976A (en) | Method for preparing graphene film | |
| CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
| CN104401977A (en) | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel | |
| CN103864062B (en) | Preparation method of graphene transparent conductive film | |
| CN106517171B (en) | A kind of preparation method of graphene aerogel | |
| CN107311158B (en) | A method of it preparing graphene film on Ni-based and is transferred to other substrates | |
| CN107425180B (en) | Three-dimensional graphene/silicon composite system, preparation method and application thereof | |
| CN102786756A (en) | Three-dimensional continuous graphene network composite material and its preparation method | |
| CN105692600B (en) | A kind of preparation method of super soft light graphite alkene Electric radiant Heating Film | |
| CN102107870A (en) | Method for quickly preparing reduced graphene by using microwaves | |
| CN104445153A (en) | Method for macroscopic quantity preparation of carbon nano coil from graphene | |
| CN104201006B (en) | A kind of Preparation method and use of CNT/manganese dioxide hydridization electrode material for super capacitor | |
| WO2012145911A1 (en) | Method for preparing graphene | |
| WO2016011905A1 (en) | Silver-doped graphene composite paper and preparation method therefor | |
| WO2012109968A1 (en) | Method for preparing modified graphene material by microwave irradiation in controlled atmosphere | |
| CN104098089A (en) | Preparation method for doped graphene foams | |
| CN106744894A (en) | A kind of preparation method of graphene powder | |
| CN102942177A (en) | Method for preparing graphene sheet | |
| CN106629685B (en) | A kind of three-dimensional graphene foam and preparation method thereof with multilevel structure | |
| CN103754878A (en) | Method for preparing carbon nano tubes on surfaces of silicon carbide particles through in-situ synthesis | |
| WO2015176220A1 (en) | Sulfur doping method for graphene | |
| CN103526182A (en) | Preparation method for nitrogen-doped graphene by utilization of nonmetal substrate surfaces | |
| CN103361065B (en) | CdSe quantum dot load Graphene with different-shape feature and uses thereof and preparation method | |
| CN102424382B (en) | Method for preparing high-specific-surface-area graphene under conditions of normal pressure and low temperature | |
| CN107188161A (en) | Graphene and 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110413 |