CN103949237B - The preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material - Google Patents
The preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material; comprise the following steps: with cellulose and urea, cyanamide or cyanic acid for raw material; by cellulose and 100: 1 ~ 1: 1000 mixing in mass ratio of urea, cyanamide or cyanic acid; then calcine under being placed in the protection of nitrogen; controlling calcination temperature range is 700 DEG C ~ 1200 DEG C, and finally naturally cooling to obtain carbon fiber and Graphene axial composite-rotor nano material.Compared with prior art, present invention process is simple, green safety and cost is low, can realize scale continuous prodution.This product is in catalysis, and energy storage, photoelectric device and sensor various fields have broad application prospects.
Description
Technical field
The invention belongs to non-metal carbon field of nanocomposite materials, be specifically related to the preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material, particularly relate to a kind of by the carbon-carbon bond connection carbon fiber of high integration and the preparation method of Graphene axial composite-rotor nano material.
Background technology
The survival and development of the mankind in day by day exhausted fossil energy and the environmental pollution serious threat be on the rise, and find and develop the focus that the renewable green energy resource substituting fossil energy becomes domestic and international using energy source and material science research.Substituting as existing energy system, the trans-utilization of solar energy is the emphasis direction of nearly scientific research decades always.Solar energy, as a kind of green energy resource, can be transformed into the energy (comprising electric energy and chemical energy) that can directly utilize by modes such as photocatalytic water, light compositing, living resources photo reversals; And these technology all depend on performance and the preparation cost of catalyst itself.In addition, energy-related energy storage technologies, as lithium ion battery, electrochemistry (super) capacitor, fuel cell and hydrogen storage material etc., also be unable to do without the exploitation of correlation function material.Cheap and the electrode material in effective thermocatalyst, photochemical catalyst and electrochemical device of preparation in macroscopic quantity is the important research target of above-mentioned numerous areas always.Material with carbon element is as a kind of distributed in nature material widely, because it is with low cost, and physicochemical properties and physical form are very abundant (contains from conductor, semiconductor is to insulator) and there is splendid stability, all show huge potentiality in fields such as catalysis, photocatalysis, electro-catalysis.
In many material with carbon elements, two-dimensional graphene shows potential using value as a kind of novel carbon nanomaterial with the electricity of its excellence, calorifics, optics and mechanical property in different field.Particularly there is high conductivity, grapheme material that high-termal conductivity, the specific area of super large, unique charge carriers give the characteristic such as mobility and high light transmittance shows extraordinary application prospect in green energy resource field.But how effectively to regulate and control and to improve the structure and fuction of Graphene, can meet the needs of high-performance catalysis material is the subject matter that current graphene-based catalyst research faces.Catalytic active center is not possessed by the perfect graphene-structured of the tightly packed bi-dimensional cellular shape formed of the monolayer carbon atom of sp2 hydridization, the mode that people adopt hetero atom (taking N as representative) to adulterate usually improves its catalytic activity, the atom N of doping can affect spin density and the distribution of charges of C atom, cause graphenic surface to produce " avtive spot ", these avtive spots can participate in catalytic reaction directly.But atom N is entrained in single-layer graphene, its fermi level moves on dirac point, and the band gap between conduction band and valence band is opened, and this will certainly affect the metalloid characteristic of its script and efficient electronic transmission performance.Therefore, how under the graphene-based catalyst of guarantee has the prerequisite of excellent conductive performance and structural stability, its maximum catalytic activity a major challenge beyond doubt to researchers is played.
As the thinnest two-dimensional material, flexible this body structure of Graphene is unstable, reunite between tending to layer by layer and form graphite-structure in pole, the active site that fine and close graphite-structure will certainly cause graphene sheet layer internal flaw to be formed is buried, causes active site to decline at double.The graphene film interlamellar spacing of reuniting reduces, and directly hinders catalytic reaction material and enters interlayer avtive spot place wherein and react, cause catalytic performance obviously to reduce.More rational solution in graphite flake layer, introduces Jie's view hole structure, the mass transfer between enhancement layer; Or by introducing graphitic carbon nano structure and Graphene compound, changing Graphene two dimension arrangement mode layer by layer originally, building graphitic carbon nano structure-graphene composite structure.The structure of graphene composite structure obviously can reduce the interface resistance of grapheme material, is conducive to the application in catalytic field particularly electro-catalysis and photoelectrocatalysis field of Graphene or class graphite material.
Summary of the invention
Object of the present invention is exactly provide the preparation method of a kind of carbon fiber by carbon-carbon bond high integration and Graphene axial composite-rotor nano material to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions: the preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material; it is characterized in that; comprise the following steps: with cellulose and urea, cyanamide or cyanic acid for raw material; by cellulose and 100: 1 ~ 1: 1000 mixing in mass ratio of urea, cyanamide or cyanic acid; then calcine under being placed in the protection of nitrogen; controlling calcination temperature range is 700 DEG C ~ 1200 DEG C, and finally naturally cooling to obtain carbon fiber and Graphene axial composite-rotor nano material.
Described cellulose is bacteria cellulose, hemicellulose, lignin or pectin.
Described urea, cyanamide or cyanic acid are urea, cyanamide, dicyandiamide, melamine or cyanuric acid.
The mass ratio of described cellulose and urea, cyanamide or cyanic acid is 1: 20.
Described calcining heat is 1000 DEG C.
Graphene, along the growth of carbon fiber both sides, forms coaxial composite structure.
Described Graphene thickness is 0.34 ~ 13nm.
In described carbon fiber and Graphene axial composite-rotor nano material, carbon nanocoils thickness is 1 ~ 500nm.
Compared with prior art, technical characterstic of the present invention is, with cellulose and urea, cyanamide or cyanic acid for raw material, in-situ carburization forms celion axial composite-rotor nitrogen-doped graphene lamellar structure (as shown in Figure 1), there is technique simple, be easy to control, green safety, and can preparation in macroscopic quantity be realized.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of carbon fiber and Graphene axial composite-rotor nano material.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
Control the mass ratio 1: 20 of bacteria cellulose and urea, bacteria cellulose and urea mixing be placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings,
bacteria cellulose andurea in-situ carburization forms celion axial composite-rotor nitrogen-doped graphene lamellar structure (as shown in Figure 1), last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material, in product, Graphene thickness is 0.34 ~ 13nm, and carbon nanocoils thickness is 1 ~ 500nm.
Embodiment 2:
Control the mass ratio 1: 20 of hemicellulose and urea, hemicellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 3:
Control the mass ratio 1: 20 of lignin and urea, lignin and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 4:
Control the mass ratio 1: 20 of pectin and urea, pectin and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 5:
Control the mass ratio 1: 20 of bacteria cellulose and cyanamide, bacteria cellulose and cyanamide mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 6:
Control the mass ratio 1: 20 of bacteria cellulose and dicyandiamide, bacteria cellulose and dicyandiamide mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 7:
Control the mass ratio 1: 20 of bacteria cellulose and melamine, bacteria cellulose and melamine mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 8:
Control the mass ratio 1: 20 of bacteria cellulose and cyanuric acid, bacteria cellulose and cyanuric acid mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 9:
Control the mass ratio 1: 20 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1500 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 10:
Control the mass ratio 1: 20 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1250 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 11:
Control the mass ratio 1: 20 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 900 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 12:
Control the mass ratio 1: 20 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 800 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 13:
Control the mass ratio 100: 1 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 14:
Control the mass ratio 10: 1 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 15:
Control the mass ratio 1: 1 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 16:
Control the mass ratio 1: 10 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 17:
Control the mass ratio 1: 100 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Embodiment 18:
Control the mass ratio 1: 1000 of bacteria cellulose and urea, bacteria cellulose and urea mixing are placed in the Muffle furnace of nitrogen protection, 1000 DEG C of calcinings, last cooling naturally obtains carbon fiber and Graphene axial composite-rotor nano material.
Claims (8)
1. the preparation method of a carbon fiber and Graphene axial composite-rotor nano material; it is characterized in that; comprise the following steps: with cellulose and material a for raw material; wherein material a is that urea, cyanamide or cyanic acid are wherein a kind of; by cellulose and material a 100:1 ~ 1:1000 mixing in mass ratio; then calcine under being placed in the protection of nitrogen, controlling calcination temperature range is 700 DEG C ~ 1200 DEG C, and finally naturally cooling to obtain carbon fiber and Graphene axial composite-rotor nano material.
2. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, described cellulose is bacteria cellulose, hemicellulose, lignin or pectin.
3. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, described material a is urea, cyanamide, dicyandiamide, melamine or cyanuric acid.
4. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, the mass ratio of described cellulose and material a is 1:20.
5. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, described calcining heat is 1000 DEG C.
6. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, Graphene, along the growth of carbon fiber both sides, forms coaxial composite structure.
7. the preparation method of a kind of carbon fiber according to claim 1 or 6 and Graphene axial composite-rotor nano material, is characterized in that, described Graphene thickness is 0.34 ~ 13nm.
8. the preparation method of a kind of carbon fiber according to claim 1 and Graphene axial composite-rotor nano material, is characterized in that, in described carbon fiber and Graphene axial composite-rotor nano material, carbon nanocoils thickness is 1 ~ 500nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104477875A (en) * | 2014-11-19 | 2015-04-01 | 上海交通大学 | Method for transforming waste paper or fiber fabric into graphene-carbon fiber composite material |
| CN104795565A (en) * | 2015-05-11 | 2015-07-22 | 内蒙古民族大学 | Porous graphene powder rich in heteroatom and preparation method and application thereof |
| CN106587019B (en) * | 2016-12-16 | 2018-07-17 | 武汉工程大学 | A kind of preparation method of lignin-base biological carbon/graphene composite nano material |
| CN107715880B (en) * | 2017-10-18 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanocomposite with non-noble metal particles anchored on graphene sheet, product and application thereof |
| CN112156801A (en) * | 2020-09-27 | 2021-01-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of nitrogen-doped axial carbon fiber/graphene-loaded cobalt nano electro-catalyst |
| CN112695342A (en) * | 2020-12-28 | 2021-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cobalt/nitrogen-doped graphene and carbon nanofiber composite material, product and application thereof |
| CN114351182A (en) * | 2021-12-23 | 2022-04-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of biomass-based nitrogen-doped graphene/carbon nanofiber axial composite material loaded with monoatomic iron, product and application |
| CN115520856A (en) * | 2022-08-19 | 2022-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material with elemental iodine and sulfur particles anchored in nitrogen-doped graphene axial plane |
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| CN102642824A (en) * | 2011-02-18 | 2012-08-22 | 株式会社东芝 | Graphite nano-carbon fiber and method of producing same |
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