CN102807210B - 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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- CN102807210B CN102807210B CN201210297890.8A CN201210297890A CN102807210B CN 102807210 B CN102807210 B CN 102807210B CN 201210297890 A CN201210297890 A CN 201210297890A CN 102807210 B CN102807210 B CN 102807210B
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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 advanced material technical field, especially relate to a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase.
Background technology
Graphene is the Two-dimensional Carbon atomic crystal of monatomic bed thickness, be six sides cellular, be considered to the basic structural unit of soccerballene, carbon nanotube and graphite: decompose the soccerballene that becomes zero dimension, curling 360 ° can to form seamless hollow tube be one dimension carbon nanotube, and stacked in parallel forms three-dimensional body phase graphite.Since within 2004, finding single-layer graphene first, Graphene is just with a series of good physics, chemical properties such as its unique optical property, outstanding heat conductivility and mechanical property and outstanding electronic conduction performances, caused scientist's extensive concern and interest greatly.
The method of preparing at present Graphene mainly contains mechanically peel method, epitaxial growth method, graphite oxidation reduction method, chemical Vapor deposition process etc. on SiC or metal substrate.Mechanically peel method is repeatedly to peel off graphene film from high orientation pyrolytic graphite by transparent photomask glue, and output is little, and production efficiency is low, and poor repeatability is only limited to Laboratory Production; Though SiC epitaxial growth method can be prepared large-area graphene film, and quality is higher, but preparation condition needs high temperature high vacuum, and starting material and technology controlling and process cost are higher; Chemical Vapor deposition process is take carbon compound as carbon source, on metallic matrix, will after carbon source pyrolytic decomposition, be deposited on matrix surface, and the graphene film of gained is to be spliced by small size graphene film, and the existence of crystal boundary can affect the performance of Graphene.
Through the literature search of prior art is found, patent publication No. CN 102409399A discloses a kind of preparation method of high-quality graphene, be open formation take single wall or multi-walled carbon nano-tubes graphene film as crystal seed, by chemical Vapor deposition process take crystal seed as core at substrate surface growing graphene, the grapheme material yardstick that this method is prepared gained is large, defect is low, but starting material carbon nanotube price is comparatively expensive, source is deficient, need carbon nanotube to open it into graphene film as crystal seed take the method such as plasma etching or chemical oxidation simultaneously, increase the triviality of experimentation.
China Patent Publication No. is that CN 1421477A discloses a kind of employing biomass resource material and waste thereof as starting material, by it being carried out after a series of processing to, finally prepare having optically anisotropic Carbonaceous mesophase.These biomass derived Carbonaceous mesophase wide material sources, cheap, environmentally friendly, be beneficial to that industry is extensive to be generated, and be different from the Carbonaceous mesophase being generated as starting material by oil, coal, its interlamellar spacing is larger comparatively speaking, and had a large amount of reports using the associated viscera of preparing graphite as the Carbonaceous mesophase of starting material generation by oil, coal, so can prepare Graphene take this biomass derived Carbonaceous mesophase as presoma.
Summary of the invention
Object of the present invention is exactly to provide a kind of preparation technology simple to operation in order to overcome the defect that above-mentioned prior art exists, preparation process less energy-consumption, can mass scale production prepare the method for Graphene by biomass derived Carbonaceous mesophase.
Object of the present invention can be achieved through the following technical solutions:
A method of being prepared Graphene by biomass derived Carbonaceous mesophase, comprises the following steps:
(1) substrate be impregnated in the ethanolic soln of certain density biomass derived Carbonaceous mesophase, after 10 minutes～2 hours, substrate taken out, be dried substrate surface attachment one deck biomass derived Carbonaceous mesophase film;
(2) substrate is heat-treated under the atmosphere protection that contains hydrogen, form graphene film build-up film on base matter surface;
(3) further base matter is placed in to alcoholic solvent after ultrasonic dispersion, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Described substrate is the one in silicon single crystal, polysilicon, mica or the quartz of sheet or powdery.
The concentration of the ethanolic soln of described biomass derived Carbonaceous mesophase is 0.01～5wt%.
The ethanolic soln of described biomass derived Carbonaceous mesophase refers to biomass derived Carbonaceous mesophase is dissolved in dehydrated alcohol and is mixed with solution, and wherein biomass derived Carbonaceous mesophase is to prepare gained according to patent of invention CN1421477A.Temperature in 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.
Other described 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 the one in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or ethylene glycol.
Described alcoholic solvent is preferably ethanol.
Biomass derived Carbonaceous mesophase is a kind of liquid crystal of condensed nucleus aromatic chemical structure, forms stratiform arrangement architecture on substrate surface.The marginal existence hydroxyl isopolarity group of its each unit, in heat treatment process, in the time that temperature raises, these polar groups are mutually assembled in the plane and polycondensation are occurred, and cause some unit to melt and become the graphene film of larger sized two dimensional crystal structure.And perpendicular to in-plane, heat-processed easily causes the interlamellar spacing of graphene film to shorten and then form graphite crystal.But under hydrogen atmosphere, hydrogen atom in hydrogen molecule can and the polar group on graphene film surface be inserted between two-layer graphene film in the mode that forms hydrogen bond, avoid between graphene film, because significantly dwindling of interlamellar spacing forms graphite crystal, having maintained the stability of graphene-structured.
Compared with prior art, the starting material that the present invention adopts are to have optically anisotropic biomass derived Carbonaceous mesophase, and its excellent property, interlamellar spacing are large, wide material sources, cheap, environmentally friendly.The present invention is the one application to biomass derived Carbonaceous mesophase, and a kind of novel preparation technology of Graphene is provided.Preparation technology of the present invention is simple to operation, and preparation process less energy-consumption can mass scale production, and the graphene film preparing and the alcosol of Graphene, can be used for solar cell, nanometer electronic device, sensor, has wide market outlook.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture that embodiment 1 prepares the graphene film build-up film of gained.
Fig. 2 is the Raman Characterization result that embodiment 2 prepares the graphene film build-up film of gained.
Fig. 3 is the atomic force microscope characterization result that embodiment 6 prepares the graphene film build-up film of gained.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.The present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Monocrystalline silicon piece be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 0.01wt%, after 30 minutes, monocrystalline silicon piece is taken out, after being at room temperature dried, adhere to one deck biomass derived Carbonaceous mesophase film at monocrystalline silicon sheet surface.Monocrystalline silicon piece is placed under pure hydrogen atmosphere protection and is heat-treated, and temperature is 600 ℃, and the time is 6 hours, forms graphene film build-up film at monocrystalline silicon sheet surface, and its transmission electron microscope photo as shown in Figure 1; Further monocrystalline silicon piece is put into ethanol after ultrasonic dispersion, prepared the ethanol colloidal sol of Graphene.
Embodiment 2
Polysilicon chip be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 0.5wt%, after 30 minutes, polysilicon chip is taken out, after being at room temperature dried, at polysilicon chip surface attachment one deck biomass derived Carbonaceous mesophase film.Polysilicon chip is placed under pure hydrogen atmosphere protection and is heat-treated, and temperature is 800 ℃, and the time is 2 hours, forms graphene film build-up film on polysilicon chip surface, and Raman spectrum as shown in Figure 2; Further polysilicon chip is put into ethylene glycol after ultrasonic dispersion, prepared the ethylene glycol colloidal sol of Graphene.
Embodiment 3
Polycrystalline silica flour be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 1wt%, after 20 minutes, polycrystalline silica flour is taken out, after being dried at 60 ℃, at polycrystalline silica flour surface attachment one deck biomass derived Carbonaceous mesophase film.Polycrystalline silica flour is placed under pure hydrogen atmosphere protection and is heat-treated, and temperature is 800 ℃, and the time is 2 hours, forms graphene film build-up film at polycrystalline silicon powder surface; Further polycrystalline silica flour is put into methyl alcohol after ultrasonic dispersion, prepare the methyl alcohol colloidal sol of Graphene.
Embodiment 4
Sheet mica be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 2wt%, after 1 hour, sheet mica is taken out, after being dried at 80 ℃, at sheet mica surface attachment one deck biomass derived Carbonaceous mesophase film.Sheet mica is placed in to hydrogen, argon gas mixed gas, and (hydrogen volume per-cent: 80%) heat-treat under protection, temperature is 1000 ℃, and the time is 1 hour, forms graphene film build-up film on sheet mica surface; Further sheet mica is put into Virahol after ultrasonic dispersion, prepared the Virahol colloidal sol of Graphene.
Embodiment 5
Quartz plate be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 2wt%, after 2 hours, quartz plate is taken out, after being at room temperature dried, at quartz plate surface attachment one deck biomass derived Carbonaceous mesophase film.Quartz plate is placed in to hydrogen, nitrogen mixture body, and (hydrogen volume per-cent: 90%) heat-treat under protection, temperature is 900 ℃, and the time is 2 hours, forms graphene film build-up film on quartz plate surface; Further quartz plate is put into propyl carbinol after ultrasonic dispersion, prepared the propyl carbinol colloidal sol of Graphene.
Embodiment 6
Quartz plate be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 5wt%, after 1 hour, quartz plate is taken out, after being dried at 100 ℃, at quartz plate surface attachment one deck biomass derived Carbonaceous mesophase film.Quartz plate is placed in to hydrogen, helium mix gas (hydrogen volume per-cent: 90%) heat-treat under protection, temperature is 900 ℃, time is 2 hours, forms graphene film build-up film on quartz plate surface, and atomic force microscope characterization result as shown in Figure 3; Further quartz plate is put into ethanol after ultrasonic dispersion, prepared the ethanol colloidal sol of Graphene.
Embodiment 7
A method of being prepared Graphene by biomass derived Carbonaceous mesophase, comprises the following steps:
(1) sheet mica be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 0.01wt%, after 2 hours by substrate take out, drying at room temperature, sheet mica surface attachment one deck biomass derived Carbonaceous mesophase 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, forms graphene film build-up film on base matter surface;
(3) further base matter is placed in to propyl carbinol after ultrasonic dispersion, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Embodiment 8
A method of being prepared Graphene by biomass derived Carbonaceous mesophase, comprises the following steps:
(1) flint be impregnated in the ethanolic soln of biomass derived Carbonaceous mesophase that concentration is 5wt%, after 10 minutes, substrate is taken out, 100 ℃ dry, surface attachment one deck biomass derived Carbonaceous mesophase 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 ℃, treatment time is 1 hour, forms graphene film build-up film on base matter surface;
(3) further base matter is placed in to Pentyl alcohol after ultrasonic dispersion, graphene film separates with base matter, forms the alcosol of Graphene, is product.
Claims (7)
1. a method of being prepared Graphene by biomass derived Carbonaceous mesophase, is characterized in that, the method comprises the following steps:
(1) substrate be impregnated in the ethanolic soln of certain density biomass derived Carbonaceous mesophase, after 10 minutes～2 hours, substrate taken out, be dried substrate surface attachment one deck biomass derived Carbonaceous mesophase film;
(2) substrate is heat-treated under the atmosphere protection that contains hydrogen, form graphene film build-up film on base matter surface;
(3) further base matter is placed in to alcoholic solvent after ultrasonic dispersion, graphene film separates with base matter, forms the alcosol of Graphene, is product;
The described atmosphere that contains hydrogen is the gas mixture of pure hydrogen, hydrogen and nitrogen or other rare gas elementes, and 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.
2. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 1, is characterized in that, described substrate is the one in silicon single crystal, polysilicon, mica or the quartz of sheet or powdery.
3. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 1, it is characterized in that, the ethanolic soln of described biomass derived Carbonaceous mesophase refers to biomass derived Carbonaceous mesophase is dissolved in and in dehydrated alcohol, is mixed with solution.
4. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 1, is characterized in that, the concentration of the ethanolic soln of described biomass derived Carbonaceous mesophase is 0.01～5wt%.
5. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 1, is characterized in that, the temperature in drying process is room temperature～100 ℃.
6. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 1, is characterized in that, described alcoholic solvent is the one in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, Pentyl alcohol or ethylene glycol.
7. a kind of method of being prepared Graphene by biomass derived Carbonaceous mesophase according to claim 6, is characterized in that, described alcoholic solvent is ethanol.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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 |
| CN107934947B (en) * | 2017-12-15 | 2021-06-08 | 广州中天联合高新技术发展有限公司 | Graphene preparation 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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| CN1421477A (en) * | 2002-12-05 | 2003-06-04 | 上海交通大学 | Prepn process of biomass derived intemediate carbon phase |
| CN1792785A (en) * | 2005-12-29 | 2006-06-28 | 上海交通大学 | Process for preparing forming active carbod by biomess derived carbonaceous medium phase |
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| US8114375B2 (en) * | 2008-09-03 | 2012-02-14 | Nanotek Instruments, Inc. | Process for producing dispersible nano graphene platelets from oxidized graphite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421477A (en) * | 2002-12-05 | 2003-06-04 | 上海交通大学 | Prepn process of biomass derived intemediate carbon phase |
| CN1792785A (en) * | 2005-12-29 | 2006-06-28 | 上海交通大学 | Process for preparing forming active carbod by biomess derived carbonaceous medium phase |
Non-Patent Citations (2)
| Title |
|---|
| Easy synthesis and characterization of high quality graphene sheets produced from mesocarbon microbeads;Ying Kong et al.;《Materials Letters》;20110530;第65卷;第2739－2741页 * |
| Ying Kong et al..Easy synthesis and characterization of high quality graphene sheets produced from mesocarbon microbeads.《Materials Letters》.2011,第65卷 |
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