CN104477875A - Method for transforming waste paper or fiber fabric into graphene-carbon fiber composite material - Google Patents
Method for transforming waste paper or fiber fabric into graphene-carbon fiber composite material Download PDFInfo
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- CN104477875A CN104477875A CN201410663239.7A CN201410663239A CN104477875A CN 104477875 A CN104477875 A CN 104477875A CN 201410663239 A CN201410663239 A CN 201410663239A CN 104477875 A CN104477875 A CN 104477875A
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Abstract
The invention relates to a method for transforming waste paper or fiber fabric into a graphene-carbon fiber composite material. The method comprises the following steps: mixing the waste paper or fiber fabric with urea, cyanamide or cyanic acid according to a mass ratio of (10:1) to (1:100) and arranging in a muffle furnace under the protection of nitrogen; treating for 1-48 hours by controlling the calcining temperature to 800 to 1500 DEG C; finally naturally cooling to obtain a graphene modified carbon fiber composite material. Compared with the prior art, the method disclosed by the invention is simple in process, environmental friendly, safe, low in cost and capable of realizing large-scale continuous production; the prepared composite material is wide in application range in various fields such as catalysis, energy storage, photo-electric parts and sensors.
Description
Technical field
The invention belongs to non-metal carbon field of nanocomposite materials, especially relate to a kind of method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite.
Background technology
The world today, waste paper recycle decreasing pollution, environmental protect, economize on resources with the energy in create huge economic benefit and environmental benefit, be realize the important aspect of paper industry Sustainable development and social sustainable development one, therefore someone is referred to as " forest in city " industry.China is world's waste paper importer of last resort and consumption big country, and the domestic waste paper rate of recovery is starkly lower than world average level, and present stage in the world developed country to the recycling of waste paper, no matter all had quite high level in scale or technically, the recycling of waste paper has progressively become a developing direction of modern paper industry.
At present, domestic waste paper recovering means mainly or by high temperature burning handling, this will certainly consume a large amount of heat energy, and the waste gas of generation equally also can pollutant atmosphere.For this reason, seek the object that a kind of effective Waste Paper Handling means can either reach utilization of waste material, can energy-saving and emission-reduction be had again, the effect of protection of the environment simultaneously.As everyone knows, the micrograde polymer fibrous reticulum that paper is interweaved by three-dimensional forms, and the surface of these polymer fibers is simultaneously containing abundant nano level chain polysaccharide, and these polymer fibers can obtain the carbon fiber paper of macroscopic view by calcining under protection of inert gas.Carbon fiber paper then can directly or modification application in different fields.
In many carbon materials, 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.The graphene-based matrix material particularly with characteristics such as high conductivity, high thermal conductivity, the specific surface area of super large, unique charge carrier mobility and high transmittances shows extraordinary application prospect in green energy resource field.So how both Graphene and carbon fiber paper are perfectly combined, and play its maximum application advantage, become a great problem of current carbon material investigators.
Chinese patent CN103949237A discloses the preparation method of a kind of carbon fiber and Graphene axial composite-rotor nano material, with Mierocrystalline cellulose and urea, cyanamide or cyanic acid are raw material, by Mierocrystalline cellulose and urea, cyanamide or cyanic acid is 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 ~ 120 DEG C, last naturally cooling cooling can obtain carbon fiber and Graphene axial composite-rotor nano material, but this patent take Mierocrystalline cellulose as raw material, the carbon fiber obtained and Graphene axial composite-rotor nano material are difficult to processed and applied.
Summary of the invention
Object of the present invention be exactly provide to overcome defect that above-mentioned prior art exists a kind of easy to process, have wide range of applications, cost-saving and utilize waste paper or the fabric that realize utilization of waste material are converted into the method for Graphene-carbon-fibre composite.
Object of the present invention can be achieved through the following technical solutions:
Waste paper or fabric is utilized to be converted into the method for Graphene-carbon-fibre composite; adopt following steps: by discarded paper or fabric and urea, cyanamide or cyanic acid in mass ratio 10: 1 ~ 1: 100 mixing be placed in the retort furnace of nitrogen protection; control calcining temperature 800 ~ 1500 DEG C process 1 ~ 48 hour, last naturally cooling obtains the carbon-fibre composite of graphene modified.
Described discarded paper is newspaper, A4 printer paper, medicated napkin, filter paper, kraft paper, wall calendar paper or rice paper.
Described fabric is non-woven fabrics, cotton thread cloth, knitting wool cloth or linen thread cloth.
Described cyanamide is cyanamide, Dyhard RU 100 or trimeric cyanamide, and described cyanic acid is tricyanic acid.
As preferred embodiment, discarded paper or the mass ratio of fabric and urea, cyanamide or cyanic acid are 1: 40.
As preferred embodiment, the calcining temperature in retort furnace is 1000 DEG C, and the calcination processing time is 12 hours.
In the matrix material prepared, Graphene thickness is 0.37-15nm, and carbon fiber thickness is 0.01-100 μm.
Compared with prior art, the present invention is with undressed discarded paper or fabric and urea, cyanamide or cyanic acid are raw material, because waste paper and fabric are interwoven by the polymeric web of micron level, and the surface of micrometer fibers is containing abundant polymer nanofiber, this special multilevel hierarchy is easy to the matrix material that original position greying forms the graphene modified carbon fiber surface of N doping, be compared with its carbon fiber of product of preparing of raw material is difficult to processing with Graphene axial composite-rotor nano material with DIRECT UTILIZATION OF CELLULOSE, the application with undressed waste paper or fabric for raw material, Graphene-carbon fiber composite carbon paper material is directly obtained by one-step calcination process.Carbon paper has large specific surface area usually, there are very strong adsorption-decomposition function, damping, purification, deodorizing, far infrared rays and negative ion usefulness, be applicable to public with covil construction in load ground and wall, carbon has suction to put regulatory function to moisture, can also suppress temperature rise and mould, microorganism procreation, play mildew-resistant, adjustment temperature unique effect.In addition, carbon paper plays support catalyst layer and stabilized electrodes structure in fuel cell electrode, also possesses and provides the several functions such as gas passage, electron channel and drainage channel for electrode reaction.Therefore cheap and effective carbon paper material has appreciable market application foreground.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of Graphene-carbon-fibre composite.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 2
The mass ratio 1: 40 of control A4 printer paper and urea, is placed in the retort furnace of nitrogen protection by the mixture of newspaper and urea, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 3
Control the mass ratio 1: 40 of medicated napkin and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 4
Control the mass ratio 1: 40 of filter paper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 5
Control the mass ratio 1: 40 of kraft paper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 6
Control the mass ratio 1: 40 of wall calendar paper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 7
Control the mass ratio 1: 40 of rice paper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 8
Control the mass ratio 1: 40 of newspaper and cyanamide, the mixture of newspaper and cyanamide is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 9
Control the mass ratio 1: 40 of newspaper and Dyhard RU 100, the mixture of newspaper and Dyhard RU 100 is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 10
Control the mass ratio 1: 40 of newspaper and trimeric cyanamide, the mixture of newspaper and trimeric cyanamide is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 11
Control the mass ratio 1: 40 of newspaper and tricyanic acid, the mixture of newspaper and tricyanic acid is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 12
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1500 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 13
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1250 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 14
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 900 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 15
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 800 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 16
Control the mass ratio 10: 1 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 17
Control the mass ratio 1: 1 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 18
Control the mass ratio 1: 10 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 19
Control the mass ratio 1: 100 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 12 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 20
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 1 hour, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 21
Control the mass ratio 1: 40 of newspaper and urea, the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection, 1000 DEG C of calcinings 24 hours, last naturally cooling obtains the matrix material of graphene modified carbon fiber surface.
Embodiment 22
Control the mass ratio 1: 40 of newspaper and urea; the mixture of newspaper and urea is placed in the retort furnace of nitrogen protection; calcine 48 hours for 1000 DEG C; last naturally cooling obtains the matrix material of graphene modified carbon fiber surface; as shown in Figure 1, about 12 μm of thick micron order carbon fiber surface uniform folds thickness is about the graphene-structured of 1.2nm to stereoscan photograph.
Claims (9)
1. utilize waste paper or fabric to be converted into the method for Graphene-carbon-fibre composite, it is characterized in that, adopt following steps:
By discarded paper or fabric and urea, cyanamide or cyanic acid in mass ratio 10: 1 ~ 1: 100 mixing be placed in the retort furnace of nitrogen protection; control calcining temperature 800 ~ 1500 DEG C process 1 ~ 48 hour, last naturally cooling obtains the carbon-fibre composite of graphene modified.
2. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, described discarded paper is newspaper, A4 printer paper, medicated napkin, filter paper, kraft paper, wall calendar paper or rice paper.
3. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, described fabric is non-woven fabrics, cotton thread cloth, knitting wool cloth or linen thread cloth.
4. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, described cyanamide is cyanamide, Dyhard RU 100 or trimeric cyanamide, and described cyanic acid is tricyanic acid.
5. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, the mass ratio of described discarded paper or fabric and urea, cyanamide or cyanic acid preferably 1: 40.
6. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, the calcining temperature in retort furnace preferably 1000 DEG C.
7. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, the preferably 12 hours treatment time in retort furnace.
8. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, in matrix material, Graphene thickness is 0.37 ~ 15nm.
9. the method utilizing waste paper or fabric to be converted into Graphene-carbon-fibre composite according to claim 1, is characterized in that, in matrix material, carbon fiber thickness is 0.01 ~ 100 μm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000556A (en) * | 2015-08-31 | 2015-10-28 | 哈尔滨工业大学 | Method for preparing graphene on large scale |
| CN105514507A (en) * | 2016-02-02 | 2016-04-20 | 陕西科技大学 | Preparation method of paper-derived micro- and nano-structure hard carbon materials |
| CN105742571A (en) * | 2016-03-30 | 2016-07-06 | 陕西科技大学 | Lithium ion battery anode material for hollow tubular structured biological carbon and preparation method of anode material |
| CN108726508A (en) * | 2018-07-07 | 2018-11-02 | 福州大学 | A kind of low cost prepares the preparation method of graphene hollow fibre |
| CN111519281A (en) * | 2020-04-29 | 2020-08-11 | 四川大学 | Method for preparing nitrogen-doped carbon fiber electrode material by using leather and electrode |
| 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 |
| CN112624093A (en) * | 2020-11-03 | 2021-04-09 | 中国科学技术大学 | Method for preparing graphene on large scale and application |
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| JP2009292676A (en) * | 2008-06-04 | 2009-12-17 | Kazuo Akagi | Method for producing carbon material and carbon material |
| CN101613100A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite |
| CN103818900A (en) * | 2014-03-19 | 2014-05-28 | 中南林业科技大学 | Method for preparing graphene by using disposable paper tableware as raw material |
| CN103949237A (en) * | 2014-05-12 | 2014-07-30 | 上海交通大学 | Preparation method of carbon fiber and graphene axial composite nanomaterial |
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Patent Citations (4)
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| JP2009292676A (en) * | 2008-06-04 | 2009-12-17 | Kazuo Akagi | Method for producing carbon material and carbon material |
| CN101613100A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite |
| CN103818900A (en) * | 2014-03-19 | 2014-05-28 | 中南林业科技大学 | Method for preparing graphene by using disposable paper tableware as raw material |
| CN103949237A (en) * | 2014-05-12 | 2014-07-30 | 上海交通大学 | Preparation method of carbon fiber and graphene axial composite nanomaterial |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000556A (en) * | 2015-08-31 | 2015-10-28 | 哈尔滨工业大学 | Method for preparing graphene on large scale |
| CN105514507A (en) * | 2016-02-02 | 2016-04-20 | 陕西科技大学 | Preparation method of paper-derived micro- and nano-structure hard carbon materials |
| CN105742571A (en) * | 2016-03-30 | 2016-07-06 | 陕西科技大学 | Lithium ion battery anode material for hollow tubular structured biological carbon and preparation method of anode material |
| CN108726508A (en) * | 2018-07-07 | 2018-11-02 | 福州大学 | A kind of low cost prepares the preparation method of graphene hollow fibre |
| CN108726508B (en) * | 2018-07-07 | 2021-10-29 | 福州大学 | Preparation method for preparing graphene hollow fiber at low cost |
| CN111519281A (en) * | 2020-04-29 | 2020-08-11 | 四川大学 | Method for preparing nitrogen-doped carbon fiber electrode material by using leather and electrode |
| 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 |
| CN112624093A (en) * | 2020-11-03 | 2021-04-09 | 中国科学技术大学 | Method for preparing graphene on large scale and application |
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Application publication date: 20150401 |