CN102807210A - Method for preparing graphene by biomass derived carbonaceous mesophase - Google Patents
Method for preparing graphene by biomass derived carbonaceous mesophase Download PDFInfo
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- CN102807210A CN102807210A CN2012102978908A CN201210297890A CN102807210A CN 102807210 A CN102807210 A CN 102807210A CN 2012102978908 A CN2012102978908 A CN 2012102978908A CN 201210297890 A CN201210297890 A CN 201210297890A CN 102807210 A CN102807210 A CN 102807210A
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Abstract
The invention relates to a method for preparing graphene by biomass derived carbonaceous mesophase. The method includes soaking base material into ethanol solution of biomass derived carbonaceous mesophase; extracting and drying the base material for a certain time; attaching a layer of biomass derived carbonaceous mesophase film to the surface of the base material; performing heat treatment to the base material under protection of hydrogen atmosphere, namely forming an accumulated graphene film on the surface of the base material; and further placing the base material to alcoholic solvent to perform ultrasonic dispersion, and separating the graphene film from the base material to obtain graphene alcosol. Preparation technology is simple, the method is easy to implement, the biomass derived carbonaceous mesophase is abundant and low in cost, energy consumption is low in the preparation process, batch large-scale production is achieved, and the prepared graphene film and graphene alcosol can be used for solar cells, nano-electronic devices, sensors and the like and have wide market prospect.
Description
Technical field
The invention belongs to the advanced material technical field, especially relate to a kind of method for preparing Graphene by the biomass derived carbonaceous mesophase mutually.
Background technology
Graphene is the two-dimentional carbon atom crystal of monatomic bed thickness; It is cellular to be six sides; The basic structural unit that is considered to soccerballene, carbon nanotube and graphite: decompose the soccerballene that becomes zero dimension; Curling 360 °, can to form seamless hollow tube be the one dimension carbon nanotube, and stacked in parallel then forms three-dimensional body phase graphite.Since finding single-layer graphene first in 2004; Graphene is just with its unique optical property, outstanding heat conductivility and mechanical property and outstanding a series of good physics, chemical properties such as electronic conduction performance, caused scientist's extensive concern and interest greatly.
The method for preparing at present Graphene mainly contains the mechanically peel method, epitaxial growth method, graphite oxidation reduction method, chemical Vapor deposition process etc. on SiC or metal substrate.The mechanically peel method is to peel off graphene film from the high orientation pyrolytic graphite repeatedly through transparent photomask glue, and output is little, and production efficiency is low, and poor repeatability is only limited to Laboratory Production; Though the SiC epitaxial growth method can be prepared large-area graphene film, and quality is higher, but preparation condition needs the high temperature high vacuum, and starting material and technology controlling and process cost are higher; Chemical Vapor deposition process is to be carbon source with the carbon compound, is being deposited on matrix surface after with the carbon source pyrolytic decomposition on the metallic matrix, and the graphene film of gained is to be spliced by the small size graphene film, and the existence of crystal boundary can influence the performance of Graphene.
Literature search through to prior art is found; Patent publication No. CN 102409399A discloses a kind of high quality preparation method of graphene, is that the graphene film of opening formation with single wall or multi-walled carbon nano-tubes is a crystal seed, is that nuclear is at substrate surface growth Graphene with the crystal seed through chemical Vapor deposition process; The grapheme material yardstick that this method prepares gained is big; Defective is low, but starting material carbon nanotube price is comparatively expensive, and the source is deficient; Needing simultaneously carbon nanotube is opened it into graphene film with methods such as plasma etching or chemical oxidations is crystal seed, has increased the loaded down with trivial details property of experimentation.
A kind of employing biomass resource material and waste thereof, finally prepare and have optically anisotropic carbonaceous mesophase phase after it is carried out a series of processing as starting material the Chinese patent publication number for CN 1421477A discloses.These biomass derived carbonaceous mesophase phase wide material sources, cheap, environmentally friendly, be beneficial to that industry is extensive to be generated; And be different from the carbonaceous mesophase phase that generates as starting material by oil, coal; Its interlamellar spacing is bigger comparatively speaking; And a large amount of reports have been arranged, so be that presoma can prepare Graphene mutually with this biomass derived carbonaceous mesophase with the associated viscera that the carbonaceous mesophase that is generated as starting material by oil, coal prepares graphite mutually.
Summary of the invention
The object of the invention is exactly to provide a kind of preparation technology simple to operation in order to overcome the defective that above-mentioned prior art exists, the less energy-consumption of preparation process, but the mass scale prodn prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase.
The object of the invention can be realized through following technical scheme:
A kind ofly prepare the method for Graphene mutually, may further comprise the steps by the biomass derived carbonaceous mesophase:
(1) substrate impregnated in the ethanolic soln of certain density biomass derived carbonaceous mesophase phase, after 10 minutes～2 hours with substrate take out, drying, substrate surface attachment one deck biomass derived carbonaceous mesophase phase film;
(2) substrate is heat-treated containing under the atmosphere protection of hydrogen, promptly form the graphene film build-up film on the base matter surface;
(3) further place alcoholic solvent behind ultra-sonic dispersion base matter, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Described substrate is a kind of in sheet or powdered silicon single crystal, polysilicon, mica or the quartz.
The concentration of the ethanolic soln of described biomass derived carbonaceous mesophase phase is 0.01～5wt%.
The ethanolic soln of described biomass derived carbonaceous mesophase phase is meant biomass derived carbonaceous mesophase phased soln is mixed with solution that in absolute ethyl alcohol wherein the biomass derived carbonaceous mesophase is to prepare gained according to patent of invention CN1421477A mutually.Temperature in the drying process is room temperature～100 ℃.
The described atmosphere that contains hydrogen is pure hydrogen., the gas mixture of hydrogen and nitrogen or other rare gas elementes.
Described other rare gas elementes comprise helium or argon gas, and wherein hydrogen volume per-cent is greater than 75%.
Described heat treated temperature is 600～1000 ℃, and the treatment time is 1～6 hour.
Described alcoholic solvent is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or the terepthaloyl moietie.
Described alcoholic solvent is preferably ethanol.
The biomass derived carbonaceous mesophase is a kind of liquid crystal of condensed nucleus aromatic chemical structure mutually, forms the stratiform arrangement architecture on the substrate surface.Its each unitary marginal existence hydroxyl isopolarity group; In heat treatment process; When temperature raise, these polar groups were assembled each other in the plane and polycondensation are taken place, and caused some unit to melt and become the graphene film of larger sized two dimensional crystal structure.And perpendicular to in-plane, heat-processed is prone to cause the interlamellar spacing of graphene film to shorten and then form graphite crystal.But under hydrogen atmosphere; Wasserstoffatoms in the hydrogen molecule can and the polar group on graphene film surface be inserted between the two-layer graphene film with the mode that forms hydrogen bond; Avoided between the graphene film having kept the stability of graphene-structured because of dwindling significantly of interlamellar spacing forms graphite crystal.
Compared with prior art, the starting material that the present invention adopts are to have optically anisotropic biomass derived carbonaceous mesophase phase, and its excellent property, interlamellar spacing are big, wide material sources, cheap, environmentally friendly.The present invention is a kind of application to biomass derived carbonaceous mesophase phase, and a kind of novel preparation technology of Graphene is provided.Preparation technology of the present invention is simple to operation, the less energy-consumption of preparation process, but mass scale prodn, and the graphene film for preparing and the alcosol of Graphene can be used for solar cell, nanometer electronic device, transmitter etc., have vast market prospect.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the graphene film build-up film of embodiment 1 preparation gained.
Fig. 2 is the Raman spectrum characterization result of the graphene film build-up film of embodiment 2 preparation gained.
Fig. 3 is the AFM characterization result of the graphene film build-up film of embodiment 6 preparation gained.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.Present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Monocrystalline silicon piece impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 0.01wt%, after 30 minutes monocrystalline silicon piece is taken out, at room temperature after the drying, adhere to one deck biomass derived carbonaceous mesophase phase film at monocrystalline silicon sheet surface.Place pure hydrogen atmosphere protection to heat-treat down monocrystalline silicon piece, temperature is 600 ℃, and the time is 6 hours, and promptly in monocrystalline silicon sheet surface formation graphene film build-up film, its transmission electron microscope photo is as shown in Figure 1; Further monocrystalline silicon piece is put into ethanol behind ultra-sonic dispersion, prepare the ethanol colloidal sol of Graphene.
Embodiment 2
Polysilicon chip impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 0.5wt%, after 30 minutes polysilicon chip is taken out, at room temperature after the drying, at polysilicon chip surface attachment one deck biomass derived carbonaceous mesophase phase film.Polysilicon chip placed under the pure hydrogen atmosphere protection heat-treat, temperature is 800 ℃, and the time is 2 hours, promptly forms the graphene film build-up film on the polysilicon chip surface, and Raman spectrum is as shown in Figure 2; Further polysilicon chip is put into terepthaloyl moietie behind ultra-sonic dispersion, prepare the terepthaloyl moietie colloidal sol of Graphene.
Embodiment 3
The polycrystalline silica flour impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 1wt%, after 20 minutes the polycrystalline silica flour is taken out, after 60 ℃ of following dryings, at polycrystalline silica flour surface attachment one deck biomass derived carbonaceous mesophase phase film.The polycrystalline silica flour placed under the pure hydrogen atmosphere protection heat-treat, temperature is 800 ℃, and the time is 2 hours, promptly forms the graphene film build-up film at the polycrystalline silicon powder surface; Further the polycrystalline silica flour is put into methyl alcohol behind ultra-sonic dispersion, prepare the methyl alcohol colloidal sol of Graphene.
Embodiment 4
Sheet mica impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 2wt%, after 1 hour sheet mica is taken out, after 80 ℃ of following dryings, at sheet mica surface attachment one deck biomass derived carbonaceous mesophase phase film.Sheet mica is placed hydrogen, argon gas mixed gas, and (hydrogen volume per-cent: 80%) heat-treat under the protection, temperature is 1000 ℃, and the time is 1 hour, promptly forms the graphene film build-up film on the sheet mica surface; Further sheet mica is put into Virahol behind ultra-sonic dispersion, prepare the Virahol colloidal sol of Graphene.
Embodiment 5
Quartz plate impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 2wt%, after 2 hours quartz plate is taken out, at room temperature after the drying, at quartz plate surface attachment one deck biomass derived carbonaceous mesophase phase film.Quartz plate is placed hydrogen, nitrogen mixture body, and (hydrogen volume per-cent: 90%) heat-treat under the protection, temperature is 900 ℃, and the time is 2 hours, promptly forms the graphene film build-up film on the quartz plate surface; Further quartz plate is put into propyl carbinol behind ultra-sonic dispersion, prepare the propyl carbinol colloidal sol of Graphene.
Embodiment 6
Quartz plate impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 5wt%, after 1 hour quartz plate is taken out, after 100 ℃ of following dryings, at quartz plate surface attachment one deck biomass derived carbonaceous mesophase phase film.Quartz plate is placed hydrogen, helium mix gas, and (hydrogen volume per-cent: 90%) heat-treat under the protection, temperature is 900 ℃, and the time is 2 hours, promptly forms the graphene film build-up film on the quartz plate surface, and the AFM characterization result is as shown in Figure 3; Further quartz plate is put into ethanol behind ultra-sonic dispersion, prepare the ethanol colloidal sol of Graphene.
Embodiment 7
A kind ofly prepare the method for Graphene mutually, may further comprise the steps by the biomass derived carbonaceous mesophase:
(1) sheet mica impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 0.01wt%, after 2 hours with substrate take out, drying at room temperature, sheet mica surface attachment one deck biomass derived carbonaceous mesophase phase film;
(2) substrate is heat-treated under the atmosphere protection of pure hydrogen, heat treated temperature is 600 ℃, and the treatment time is 6 hours, promptly forms the graphene film build-up film on the base matter surface;
(3) further place propyl carbinol behind ultra-sonic dispersion base matter, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Embodiment 8
A kind ofly prepare the method for Graphene mutually, may further comprise the steps by the biomass derived carbonaceous mesophase:
(1) flint impregnated in the ethanolic soln of biomass derived carbonaceous mesophase phase that concentration is 5wt%, after 10 minutes with substrate take out, 100 ℃ of dryings, surface attachment one deck biomass derived carbonaceous mesophase phase film of flint;
(2) substrate is heat-treated under the atmosphere protection of helium and hydrogen (hydrogen volume per-cent is greater than 75%), heat treated temperature is 1000 ℃, and the treatment time is 1 hour, promptly forms the graphene film build-up film on the base matter surface;
(3) further place Pentyl alcohol behind ultra-sonic dispersion base matter, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Claims (10)
1. one kind prepares the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that this method may further comprise the steps:
(1) substrate impregnated in the ethanolic soln of certain density biomass derived carbonaceous mesophase phase, after 10 minutes～2 hours with substrate take out, drying, substrate surface attachment one deck biomass derived carbonaceous mesophase phase film;
(2) substrate is heat-treated containing under the atmosphere protection of hydrogen, promptly form the graphene film build-up film on the base matter surface;
(3) further place alcoholic solvent behind ultra-sonic dispersion base matter, graphene film separates with base matter, forms the alcosol of Graphene, is product.
2. according to claim 1ly a kind ofly prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that, described substrate is a kind of in sheet or powdered silicon single crystal, polysilicon, mica or the quartz.
3. a kind of method for preparing Graphene by the biomass derived carbonaceous mesophase mutually according to claim 1; It is characterized in that the ethanolic soln of described biomass derived carbonaceous mesophase phase is meant biomass derived carbonaceous mesophase phased soln is mixed with solution in absolute ethyl alcohol.
4. according to claim 1ly a kind ofly prepare the method for Graphene mutually, it is characterized in that the concentration of the ethanolic soln of described biomass derived carbonaceous mesophase phase is 0.01～5wt% by the biomass derived carbonaceous mesophase.
5. according to claim 1ly a kind ofly prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that, the temperature in the drying process is room temperature～100 ℃.
6. according to claim 1ly a kind ofly prepare the method for Graphene mutually, it is characterized in that the described atmosphere that contains hydrogen is the gas mixture of pure hydrogen, hydrogen and nitrogen or other rare gas elementes by the biomass derived carbonaceous mesophase.
7. according to claim 6ly a kind ofly prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that described other rare gas elementes comprise helium or argon gas, wherein hydrogen volume per-cent is greater than 75%.
8. according to claim 1ly a kind ofly prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that described heat treated temperature is 600～1000 ℃, the treatment time is 1～6 hour.
9. according to claim 1ly a kind ofly prepare the method for Graphene mutually by the biomass derived carbonaceous mesophase, it is characterized in that, described alcoholic solvent is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or the terepthaloyl moietie.
10. according to claim 9ly a kind ofly prepare the method for Graphene mutually, it is characterized in that described alcoholic solvent is preferably ethanol by the biomass derived carbonaceous mesophase.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150133568A1 (en) * | 2013-11-12 | 2015-05-14 | Shanghai Switchdiy Digital Technology Co., Ltd. | Method for preparing graphene from biomass-derived carbonaceous mesophase |
| CN104724696A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene by taking biomass as raw material |
| CN106315543A (en) * | 2015-06-26 | 2017-01-11 | 航天金洲（北京）能源科技有限公司 | Method of extracting and preparing compound carbon-alkene material from plants |
| CN106276909B (en) * | 2015-06-26 | 2018-03-30 | 航天金洲（北京）能源科技有限公司 | A kind of method that carbene material is extracted from plant |
| CN107934947A (en) * | 2017-12-15 | 2018-04-20 | 广州中天联合高新技术发展有限公司 | A kind of graphene production method based on efficient surfactant |
| US10549997B2 (en) | 2016-11-07 | 2020-02-04 | Council Of Scientific & Industrial Research | Process for the production of graphene sheets with tunable functionalities from seaweed promoted by deep eutectic solvents |
| CN114835108A (en) * | 2022-05-07 | 2022-08-02 | 浙江大学杭州国际科创中心 | Natural biomass-derived graphene with controllable layer number and preparation method thereof |
| WO2024031194A1 (en) * | 2022-08-12 | 2024-02-15 | Bio Graphene Solutions Inc. | Process for producing a material comprising graphene and/or graphite on a matrix, and materials prepared therefrom |
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| YING KONG ET AL.: "Easy synthesis and characterization of high quality graphene sheets produced from mesocarbon microbeads", 《MATERIALS LETTERS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150133568A1 (en) * | 2013-11-12 | 2015-05-14 | Shanghai Switchdiy Digital Technology Co., Ltd. | Method for preparing graphene from biomass-derived carbonaceous mesophase |
| US9249026B2 (en) * | 2013-11-12 | 2016-02-02 | Shanghai Jiaotong University | Method for preparing graphene from biomass-derived carbonaceous mesophase |
| CN104724696A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene by taking biomass as raw material |
| CN106315543A (en) * | 2015-06-26 | 2017-01-11 | 航天金洲（北京）能源科技有限公司 | Method of extracting and preparing compound carbon-alkene material from plants |
| CN106276909B (en) * | 2015-06-26 | 2018-03-30 | 航天金洲（北京）能源科技有限公司 | A kind of method that carbene material is extracted from plant |
| CN106315543B (en) * | 2015-06-26 | 2018-03-30 | 航天金洲（北京）能源科技有限公司 | It is a kind of that the method for preparing compound carbene material is extracted from plant |
| US10549997B2 (en) | 2016-11-07 | 2020-02-04 | Council Of Scientific & Industrial Research | Process for the production of graphene sheets with tunable functionalities from seaweed promoted by deep eutectic solvents |
| CN107934947A (en) * | 2017-12-15 | 2018-04-20 | 广州中天联合高新技术发展有限公司 | A kind of graphene production method based on efficient surfactant |
| CN114835108A (en) * | 2022-05-07 | 2022-08-02 | 浙江大学杭州国际科创中心 | Natural biomass-derived graphene with controllable layer number and preparation method thereof |
| WO2024031194A1 (en) * | 2022-08-12 | 2024-02-15 | Bio Graphene Solutions Inc. | Process for producing a material comprising graphene and/or graphite on a matrix, and materials prepared therefrom |
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| CN102807210B (en) | 2014-06-25 |
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