CN105236384A - Method for preparing three dimensional graphene/carbon nanotube ultra-light structure - Google Patents
Method for preparing three dimensional graphene/carbon nanotube ultra-light structure Download PDFInfo
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- CN105236384A CN105236384A CN201510644664.6A CN201510644664A CN105236384A CN 105236384 A CN105236384 A CN 105236384A CN 201510644664 A CN201510644664 A CN 201510644664A CN 105236384 A CN105236384 A CN 105236384A
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Abstract
A method for preparing a three dimensional graphene/carbon nanotube ultra-light structure realizes in situ growth of carbon nanotubes on three dimensional graphene foam through combining a impregnation technology with a plasma enhanced chemical vapor deposition (PECVD) technology in order to obtain the three dimensional graphene/carbon nanotube ultra-light structure. Additionally, the growth behavior of the carbon nanotubes on the three dimensional graphene foam can be regulated through adjusting an impregnation solution and parameters of the PECVD technology. The method for preparing the three dimensional graphene/carbon nanotube ultra-light structure ensures the integrity of a three dimensional skeleton structure, has the advantages of simple process, short period, high yield, low cost and environmental protection, and can realize industrial batch production.
Description
Technical field
The invention belongs to novel material and preparing technical field thereof, particularly relate to a kind of quick, convenient method preparing three-dimensional grapheme/carbon nanotube Superlight body.
Background technology
Three-dimensional graphene foam is a kind of porous class A foam A structure built by two-dimensional graphene, it utilizes the high electron mobility of Graphene, bigger serface, good mechanical strength and heat conductivility, be widely studied in fields such as energy storage, electromagnetic shielding, matrix material enhancing and catalytic materials.And how to improve the emphasis that the mechanical strength of three-dimensional graphene foam and electric property remain domestic and international investigator research further.
At present, the carbon nanotube of one dimension is prepared three-dimensional grapheme/carbon nanotube structure with the Graphene of two dimension by chemical action (huge legendary turtle closes key, covalent linkage) and physical action (hydrogen bond etc.) compound and there has been a large amount of report.Wherein, the research forming interspersed network structure body by self-assembly about carbon nanotube and Graphene is the most ripe, but this method fails fully to represent the superior mechanics of bi-material and optical, electrical performance.On the one hand, the carbon nanomaterial mixing of two kinds of dimensions can only slow down reunion to a certain extent, and can not avoid reuniting, and this is by the overall mechanical property of restriction three-dimensional grapheme/carbon nanotube structure; On the other hand, the Graphene of functionalization and carbon nanotube is utilized to carry out the structure of complex structure body, construction inner bonding action can be increased, improve the mechanical property of structure, but functionalization destroys material self structure, certainly will affect the application of three-dimensional grapheme/carbon nanotube structure in optical, electrical field.In recent years, existing document proposes to utilize chemical vapour deposition (CVD) technology to prepare Graphene and carbon nanotube three-dimensional structure material, but the magnetron sputtering that the method adopts or electron beam evaporation technique can only at graphenic surface deposition of carbon nanotubes growth catalysts, namely carbon nanotube can only grow on three-dimensional graphene foam top layer, can not prepare inside and outside homogeneous three-dimensional grapheme/carbon nanotube structure.And this method preparation technology relative complex, higher to temperature requirement, be not suitable for large-scale production.Therefore, preparing high performance three-dimensional graphene/carbon nano-tube Superlight body simply, is efficiently the current difficult problem run into.
Summary of the invention
The invention provides a kind of method simply efficiently preparing three-dimensional grapheme/carbon nanotube Superlight body.It is the efficient adsorption effect utilizing three-dimensional graphene foam, three-dimensional graphene foam is flooded in Catalyst precursor solutions, complex catalyst precursor physical efficiency is impelled to be evenly distributed in three-dimensional graphene foam structure, after super-dry, by PECVD catalyst precursor decomposed and reduce, make carbon nanotube growth in situ on grapheme foam matrix, form three-dimensional grapheme/carbon nanotube Superlight body.
Technical scheme of the present invention is realized by following steps:
(1) three-dimensional graphene foam is put into the Catalyst precursor solutions prepared in advance and flood for some time, drying is placed in the sample table of plasma activated chemical vapour deposition (PECVD) system vacuum chamber;
(2) close vacuum chamber and vacuumize, after being reduced to certain vacuum degree, pass into hydrogen to vacuum chamber and be stabilized in certain pressure intensity, specimen heating holder, catalyst precursor is decomposed, then open plasma source, apply certain power and keep for some time, impel catalyst precursor reduction in three-dimensional graphene foam;
(3) under certain temperature and power, regulate hydrogen flowing quantity and pass into hydrocarbon polymer as carbon source by certain flow, under this pressure, react for some time, make carbon nanotube in grapheme foam surface growth, thus obtained three-dimensional grapheme/carbon nanotube Superlight body.
In above-mentioned steps (1), three-dimensional graphene foam used has adsorption to Catalyst precursor solutions, Catalyst precursor solutions is the labile single or composition metal salt such as iron, cobalt, nickel, copper, chromium or organometallics, dipping time is greater than 0.5h, drying means can select lyophilize, supercritical drying, vacuum-drying, the methods such as a conventional oven is dry.
In above-mentioned steps (2), vacuum tightness is less than 0.1Pa, and hydrogen flowing quantity is 10 ~ 200sccm, and pressure is 100 ~ 500Pa, sample table temperature is 200 ~ 500 DEG C, the presoma resolving time controls at 0.5 ~ 3h, and power setting is 50 ~ 500W, and maintains 0.5 ~ 3h.
Control temperature 300 ~ 800 DEG C in above-mentioned steps (3), power adjustment 50 ~ 500W, hydrocarbon polymer (the single or binary gas of methane, ethene, acetylene, purity is greater than 99.9%) flow is 10 ~ 200sccm, pressure is 10 ~ 1000Pa, reaction times 0.5 ~ 5h.
The method not only achieve at a lower temperature carbon nanotube on three-dimensional graphene foam matrix growth in situ, and in carbon nanotube growth process, still keep the integrity of three-dimensional structure.The method preparation cost is low, and technique is simple, and gained three-dimensional grapheme/carbon nanotube Superlight height is led, high-strength, especially expands the application of three-dimensional carbon nano material in fields such as optical, electrical, matrix material enhancings.
Embodiment
Below in conjunction with specific embodiment, the method preparing three-dimensional grapheme/carbon nanotube Superlight body that to combine with PECVD technology of pickling process in the present invention is described in detail.
Embodiment 1:
Three-dimensional graphene foam is prepared, by this three-dimensional graphene foam at Catalyst precursor solutions (M by hydrothermal method
nickelous nitrate: M
magnesium nitrate=1: 1, C
nickelous nitrate=0.1mol/mL) in dipping 0.5h, with after liquid nitrogen pre-freeze at-50 DEG C vacuum lyophilization.The sample of gained drying is placed in the sample table of PECVD system vacuum chamber, closes vacuum chamber and vacuumizes, when vacuum tightness is less than 0.1Pa, hydrogen is passed into the flow of 20sccm, and to control pressure be 100Pa, specimen heating holder to 300 DEG C maintains 1h, makes Ni (N0
3)
2with Mg (N0
3)
2decomposition and inversion is NiO and MgO.Open plasma source, Modulating Power 300W also keeps 1h, impels in three-dimensional graphene foam and generates Ni/Mg0 catalyst system.Holding temperature, power and hydrogen flowing quantity are constant, pass into methane gas by 50sccm, make carbon nanotube at grapheme foam surface growth 2h, thus obtain three-dimensional grapheme/carbon nanotube Superlight body.
Embodiment 2:
Utilize template synthesis three-dimensional graphene foam, by this three-dimensional grapheme bubble at Catalyst precursor solutions (C
copper sulfate=0.5mol/mL) middle dipping 12h.Take out after sample drying, be placed in the sample table of PECVD system vacuum chamber, close vacuum chamber and be evacuated to vacuum tightness and be less than 0.1Pa.Pass into hydrogen with the flow of 50sccm, control pressure is 200Pa, and specimen heating holder to 400 DEG C maintains 1h.Apply 200W power, keep 1h, after catalyst system is formed, be warming up to 450 DEG C, power and hydrogen flowing quantity invariable, passing into acetylene gas by 100sccm makes carbon nanotube at grapheme foam surface growth 1h, namely obtains three-dimensional grapheme/carbon nanotube Superlight body.
Embodiment 3:
Adopt chemical vapour deposition (CVD) technology to prepare three-dimensional graphene foam, product is immersed in Catalyst precursor solutions (C
nickel acetate=0.8mol/mL) middle 5h.After the sample oven drying taken out, put in the sample table of PECVD system vacuum chamber, close vacuum chamber and be evacuated to vacuum tightness and be less than 0.1Pa.Pass into hydrogen, control flow 100sccm, pressure 300Pa.Sample table maintains 1h at 500 DEG C, then applies 500W power, raised temperature to 600 DEG C after constant 1.5h, power invariability is constant, hydrogen flowing quantity is adjusted to 200sccm, passes into methane/acetylene gas mixture by 200sccm, obtains three-dimensional grapheme/carbon nanotube Superlight body after 2h.
Claims (4)
1. prepare a method for three-dimensional grapheme/carbon nanotube Superlight body, it is characterized in that, comprise the following steps:
(1) three-dimensional graphene foam is put into the Catalyst precursor solutions prepared in advance and flood for some time, drying is placed in the sample table of plasma activated chemical vapour deposition (PECVD) system vacuum chamber;
(2) close vacuum chamber and be evacuated down to certain vacuum degree, passing into hydrogen, adjustment pressure post-heating sample table, catalyst precursor is decomposed, then open plasma source, apply certain power and keep for some time, impel the catalyst system needed for carbon nano tube growth to be formed;
(3) under certain temperature and power, regulate hydrogen flowing quantity and pass into hydrocarbon polymer as carbon source by certain flow, under this pressure, react for some time, make carbon nanotube in three-dimensional graphene foam surface growth, thus obtained three-dimensional grapheme/carbon nanotube Superlight body.
2. preparation method according to claim 1, it is characterized in that, three-dimensional graphene foam has adsorption to Catalyst precursor solutions, Catalyst precursor solutions is the labile single or composition metal salt such as iron, cobalt, nickel, copper, chromium or organometallics, dipping time is greater than 0.5h, and drying means can select lyophilize, supercritical drying, vacuum-drying, the methods such as a conventional oven is dry.
3. preparation method according to claim 1, it is characterized in that, low vacuum passes into hydrogen after 0.1Pa, and hydrogen flowing quantity is 10 ~ 200sccm, pressure is 100 ~ 500Pa, and sample table temperature is 200 ~ 500 DEG C, and the presoma resolving time controls at 0.5 ~ 3h, power 50 ~ 500W, and maintain 0.5 ~ 3h.
4. preparation method according to claim 1, it is characterized in that, control temperature 300 ~ 800 DEG C, apply power 50 ~ 500W, hydrocarbon polymer (the single or binary gas of methane, ethene, acetylene, purity is greater than 99.9%) flow is 10 ~ 200sccm, pressure is 10 ~ 1000Pa, reaction times 0.5 ~ 5h.
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Cited By (8)
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| CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
| CN106219532A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof |
| CN106219531A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
| CN106629690A (en) * | 2016-09-28 | 2017-05-10 | 天津工业大学 | Method for reinforcing three-dimensional graphene porous material structure |
| CN110418564A (en) * | 2019-07-23 | 2019-11-05 | 天津大学 | The preparation method of carbon nanotube and the three-dimensional carbon absorbing material of metal nanoparticle modification |
| CN111170310A (en) * | 2020-01-15 | 2020-05-19 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN113121961A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | MFS @ CNT epoxy resin composite material and preparation method thereof |
| CN113831130A (en) * | 2021-09-28 | 2021-12-24 | 安徽弘昌新材料有限公司 | Light high-strength heat preservation felt and preparation method and application thereof |
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| CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185885A (en) * | 2016-06-30 | 2016-12-07 | 天津大学 | There is isotropism height heat conduction, elastic three-dimensional grapheme and the preparation method of carbon nano tube compound material |
| CN106219532A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof |
| CN106219531A (en) * | 2016-07-29 | 2016-12-14 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
| CN106219532B (en) * | 2016-07-29 | 2018-12-07 | 碳元科技股份有限公司 | A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof |
| CN106219531B (en) * | 2016-07-29 | 2018-12-25 | 碳元科技股份有限公司 | A kind of preparation method of graphite/nanometer carbon pipe array composite heat conduction film |
| CN106629690A (en) * | 2016-09-28 | 2017-05-10 | 天津工业大学 | Method for reinforcing three-dimensional graphene porous material structure |
| CN110418564A (en) * | 2019-07-23 | 2019-11-05 | 天津大学 | The preparation method of carbon nanotube and the three-dimensional carbon absorbing material of metal nanoparticle modification |
| CN111170310A (en) * | 2020-01-15 | 2020-05-19 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN111170310B (en) * | 2020-01-15 | 2022-02-25 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN113121961A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | MFS @ CNT epoxy resin composite material and preparation method thereof |
| CN113121961B (en) * | 2021-04-20 | 2022-05-31 | 安徽大学 | MFS @ CNT epoxy resin composite material and preparation method thereof |
| CN113831130A (en) * | 2021-09-28 | 2021-12-24 | 安徽弘昌新材料有限公司 | Light high-strength heat preservation felt and preparation method and application thereof |
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Application publication date: 20160113 |