CN102086034A - Carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and preparation method - Google Patents

Carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and preparation method Download PDF

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CN102086034A
CN102086034A CN 201010590224 CN201010590224A CN102086034A CN 102086034 A CN102086034 A CN 102086034A CN 201010590224 CN201010590224 CN 201010590224 CN 201010590224 A CN201010590224 A CN 201010590224A CN 102086034 A CN102086034 A CN 102086034A
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carbon
catkin
tube
nano
poplar
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CN 201010590224
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Chinese (zh)
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CN102086034B (en
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黄维
马延文
范曲立
赵进
张玲榕
李娟娟
蒋旭
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南京邮电大学
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Abstract

The invention discloses a carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and a preparation method. The carbon-nano-tube is prepared from poplar catkin and willow catkin as raw materials by using a carbonization method. The obtained carbon-nano-tube has the external diameter of 2-20 microns and the wall thickness of approximate 0.1-1.0 micron. The method for preparing the carbon-nano-tube comprises the following steps of: putting the poplar catkin or the willow catkin in a middle area of a silica tube in a tubular furnace, and increasing the temperature to 250-2000 DEG C under the inert atmosphere; and carbonizing for 10-180 min and naturally cooling to a room temperature under the inert atmosphere to obtain a product. Compared with an artificially synthesized carbon-nano-tube, the preparation method provided by the invention has the advantages of simple and convenient process, environmental protection, and the like, the prepared carbon-nano-tube presents favorable performance in aspects of catalytic oxygen reduction reaction, electrochemical capacitors, and the like and can be used as electrodes of fuel batteries and super capacitors. In addition, the prepared carbon-nano-tube has potential application values in aspects of ion batteries, drug delivery, microreactors, and the like.

Description

With poplar wadding and catkin is the carbon micron tube and the preparation method of feedstock production
Technical field
The present invention relates to being feedstock production carbon micron tube and method with poplar wadding and catkin.
Background technology
Pass through arc discharge method [S.Iijima since the nineties in last century first by Japanese scientist Ijima, Nature, 1991,354,56.] obtained since the carbon nanotube, carbon nanotube is because of its special structure and be subjected to scientist's extensive concern and research in aspect special performances such as mechanics, electricity, calorifics, optics.The synthetic method of carbon current nanotube mainly contains arc process [T.W.Ebbesen, P.M.Ajayan, Nature, 1992,358,220.], laser evaporation method [T.Guo, R.E.Smalley.et.al., J.Phys.Chem., 1995,99,10694.], chemical Vapor deposition process [R.Andrews, D.Jacques, D.L.Qian and T.Rantell, Acc.Chem.Res., 2002,35,1008.].Chemical Vapor deposition process is lower because of its temperature of reaction, equipment is simple, carbon source kind is abundant, cost is low, output is big, can realize that suitability for industrialized production becomes the maximum carbon nanotube synthetic method of research.But limit its application at aspects such as drug delivery, microreactors because of the nano-scale of carbon nanotube, the research that therefore launches the bigger carbon micron tube of caliber is significant.
The research of carbon current micron tube is less relatively, and is main still by the artificial synthesis acquisition, as chemical Vapor deposition process [P.Meduri, J.H.Kim, H.B.Russell, J.Jasinski, G.U.Sumanasekera and M.K.Sunkara, J.Phys.Chem.C, 2010,114,10621.], template [C.C.Han, J.T.Lee, R.W.Yang, H.Chang and C.H.Han, Chem.Mater.., 1999,11,1806.] etc.And for the carbon material of diameter at micro-meter scale, can be by carbonization filamentous organisms matter such as silk [L.Deng, S.J.Guo, M.Zhou, L.Liu, C.Liuand S.J.Dong, Biosens.Bioelectron., 2010,25,2189.] and cotton preparation.But at present people still fail to find the suitable biomass presoma that carbonization prepares carbon micron tube that is used for, but plurality of advantages such as that the preparation method of even now has is easy, environmental protection, cheapness and mass-producing.Therefore, if can realize with the natural biomass being that raw material directly prepares carbon micron tube, will greatly promote the performance development and the product marketization of this class carbon material.The present invention is that feedstock production goes out carbon micron tube with poplar wadding and catkin.We know that the size of poplar wadding and catkin fiber becomes serious air pollutant at micron order because of its respiratory system to humans and animals is harmful.Therefore, the present invention has realized providing practicable solution route to the resource utilization of catkin and poplar wadding pollutent to this class problem of environmental pollution when obtaining to have the carbon micron tube of important application prospect.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of is the carbon micron tube and the preparation method of feedstock production with poplar wadding and catkin simply.It is characterized in that directly utilizing deleterious catkin of human respiratory and poplar wadding are prepared carbon micron tube for the direct carbonization of raw material.
Technical scheme: the present invention is achieved through the following technical solutions:
The carbon micron tube that with poplar wadding and catkin is feedstock production is a raw material with poplar wadding and catkin, direct carbonization acquisition under protection of inert gas; The carbon content of this carbon micron tube is 80%~95%, and nitrogen content is 1.0%~4.0%, and oxygen level is 3.0%~15%, and phosphorus content is 0.2%~2.0%; External diameter is 2~20 μ m, and thickness of pipe is 0.1~1.0 μ m.
Preparation process comprises the steps:
Catkin or poplar wadding is placed the silica tube region intermediate of tube furnace, under inert atmosphere, be warming up to 250~2000 ℃, under inert atmosphere, naturally cool to room temperature behind carbonization 10~180min and obtain product.
Described carbon micron tube has good catalytic oxidation-reduction reactivity worth, can be used for the fuel cell electrode material.
Described carbon micron tube has good capacitance characteristic, can be used for the electrode materials of ultracapacitor.
Beneficial effect: characteristics of the present invention are to utilize deleterious catkin of humans and animals respiratory system and poplar wadding are prepared carbon micron tube for the direct carbonization of raw material, have advantages such as simple, quick, efficient and environmental protection.
The prepared carbon micron tube of the present invention has good catalytic oxidation-reduction reactivity worth and capacitance characteristic, can be used as the electrode materials of fuel cell and ultracapacitor.
Description of drawings
The x-ray photoelectron spectroscopy spectrogram of the carbon micron tube that obtains under 950 ℃ among Fig. 1: the embodiment 1.
Fig. 2: among catkin (a) and the embodiment 1 550 ℃ (b), 750 ℃ (c) and 950 ℃ (d) carbonization down
The X-ray diffraction spectrum of the carbon micron tube that obtains.
Fig. 3: among catkin (a) and the embodiment 1 550 ℃ (b), 750 ℃ (c) and 950 ℃ (d) down the carbon micron tube that obtains of carbonization Raman spectrum.
The linear volt-ampere curve figure of the rotating disk electrode of carbon micron tube among Fig. 4: the embodiment 3.
The linear volt-ampere curve figure of the rotating-disk round loop electrode of carbon micron tube among Fig. 5: the embodiment 3.
Cyclic voltammogram among Fig. 6: the embodiment 5.
Constant current charge-discharge figure among Fig. 7: the embodiment 5.
Alternating-current impedance figure among Fig. 8: the embodiment 5.
Embodiment
Carbon micron tube is by poplar wadding or catkin being placed argon atmosphere, be warming up to 250~2000 ℃, naturally cooling to room temperature behind carbonization 10~180min under argon shield and obtain product.
Embodiment 1 places the 100mg catkin region intermediate of horizontal pipe furnace silica tube; under the argon shield atmosphere; temperature rise rate with 1~30 ℃/min is heated to 250~2000 ℃ of temperature of reaction, naturally cools to room temperature behind carbonization 10~180min and obtain product under the argon shield atmosphere.
Embodiment 2 places the 100mg catkin region intermediate of horizontal pipe furnace silica tube; under the argon shield atmosphere; temperature rise rate with 1~30 ℃/min is heated to 250~2000 ℃ of temperature of reaction, naturally cools to room temperature behind carbonization 1~180min and obtain product under the argon shield atmosphere.
The carbon micron tube that 3750 ℃ of following carbonization catkin 60min of embodiment obtain, for testing its catalytic oxidation-reduction reactivity worth, at the 25 ℃ of linear volt-ampere curve figure (RED) of rotating disk electrode and linear volt-ampere curve figure (RRED) of rotating-disk round loop electrode that test above-mentioned carbon micron tube down with CHI 760C electrochemical workstation.The carbon micron tube 5mg ultra-sonic dispersion of obtaining obtains the 1.0mg/mL catalyst solution in 5mL water, the catalyzer solvent (40 μ L) that obtains is added drop-wise on the surface of glass-carbon electrode, drip the Nafion of 0.5 μ L under the room temperature after the drying again, place 12h at room temperature to complete drying, test is carried out in oxygen-saturated 1mol/L NaOH electrolytic solution.Test result shows that this material has good catalytic oxidation-reduction reactivity worth.
The carbon micron tube that 4950 ℃ of following carbonization poplar wadding 60min of embodiment obtain, for testing its catalytic oxidation-reduction reactivity worth, at the 25 ℃ of linear volt-ampere curve (RED) of rotating disk electrode and linear volt-ampere curves (RRED) of rotating-disk round loop electrode of testing above-mentioned carbon micron tube down with CHI 760C electrochemical workstation.The carbon micron tube 5mg ultra-sonic dispersion of obtaining obtains the 1.0mg/mL catalyst solution in 5mL water, the catalyzer solvent (40 μ L) that obtains is added drop-wise on the surface of glass-carbon electrode, drip the Nafion of 0.5 μ L under the room temperature after the drying again, place 12h at room temperature to complete drying, test is carried out in oxygen-saturated 1mol/L NaOH electrolytic solution.Test result shows that this material has good catalytic oxidation-reduction reactivity worth.
The carbon micron tube that 5750 ℃ of following carbonization poplar wadding 60min of embodiment obtain, for testing its capacitance characteristic, the carbon micron tube 50mg that obtains, and about 2.6mg polytetrafluoroethylene (PTFE) emulsion is to the agate mortar the inside, add an amount of dehydrated alcohol again, grind evenly to becoming film like.An amount of film spread upon use dehydrated alcohol ultrasonic cleaning and drying 1 * 2cm completely in advance 2The one side of nickel foam on, press down agreement that contracts a film or TV play to an actor or actress 30s at 100MPa, then at 120 ℃ of dry 12h, claim to such an extent that the quality of its active material is approximately 5~10mg.As working electrode, platinum filament is a counter electrode with prepared electrode, and saturated calomel electrode is a reference electrode, in 6mol/L KOH solution, and its cyclic voltammogram of test, constant current charge-discharge figure, alternating-current impedance figure on CHI 660C electrochemical workstation.Test result shows that this carbon micron tube has capacitance characteristic preferably.
The carbon micron tube that 6750 ℃ of following carbonization catkin 60min of embodiment obtain, for testing its capacitance characteristic, the carbon micron tube 50mg that obtains, and about 2.6mg polytetrafluoroethylene (PTFE) emulsion is to the agate mortar the inside, add an amount of dehydrated alcohol again, grind evenly to becoming film like.An amount of film spread upon use dehydrated alcohol ultrasonic cleaning and drying 1 * 2cm completely in advance 2The one side of nickel foam on, press down agreement that contracts a film or TV play to an actor or actress 30s at 100MPa, then at 120 ℃ of dry 12h, claim to such an extent that the quality of its active material is approximately 5~10mg.As working electrode, platinum filament is a counter electrode with prepared electrode, and saturated calomel electrode is a reference electrode, in 6mol/L KOH solution, and its cyclic voltammogram of test, constant current charge-discharge figure, alternating-current impedance figure on CHI 660C electrochemical workstation.Test result shows that this carbon micron tube has capacitance characteristic preferably.

Claims (2)

1. one kind is the carbon micron tube of feedstock production with poplar wadding and catkin, it is characterized in that this carbon micron tube is a raw material with poplar wadding and catkin, and directly carbonization obtains under protection of inert gas; The carbon content of this carbon micron tube is 80%~95%, and nitrogen content is 1.0%~4.0%, and oxygen level is 3.0%~15%, and phosphorus content is 0.2%~2.0%; External diameter is 2~20 μ m, and thickness of pipe is 0.1~1.0 μ m.
2. want 1 as right to ask described be the preparation method of the carbon micron tube of feedstock production with poplar wadding and catkin for one kind, it is characterized in that preparation process comprises the steps:
Catkin or poplar wadding is placed the silica tube region intermediate of tube furnace, under inert atmosphere, be warming up to 250~2000 ℃, under inert atmosphere, naturally cool to room temperature behind carbonization 10~180min and obtain product.
CN201010590224A 2010-12-13 2010-12-13 Carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and preparation method CN102086034B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557026A (en) * 2011-11-09 2012-07-11 南京邮电大学 Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material
CN103253649A (en) * 2013-04-19 2013-08-21 东南大学 Preparation method and application of carbon sponge
CN103950916A (en) * 2014-04-24 2014-07-30 合肥国轩高科动力能源股份公司 Preparation method of carbonaceous anode material for lithium ion batteries
CN104916451A (en) * 2015-05-08 2015-09-16 中国科学院山西煤炭化学研究所 Method for preparing super capacitor electrode material made of nickel oxide nanosheet grown on micro carbon tube
CN105609320A (en) * 2016-03-02 2016-05-25 中国科学院山西煤炭化学研究所 Preparation method for biomass-based hollow carbon microtube/Ni-Co metal sulfide composite electrode material
RU2611509C2 (en) * 2015-06-19 2017-02-27 Нина Александровна Попова Method of producing single-layer carbon micro- and nanotubes
CN106744784A (en) * 2015-11-18 2017-05-31 中国海洋大学 A kind of dipping-activation method prepares method of nitrogen oxygen codope Enteromorpha basic unit secondary aperture carbon material and application thereof
CN108862235A (en) * 2018-06-07 2018-11-23 上海大学 A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode
CN110002429A (en) * 2019-05-09 2019-07-12 中国科学院山西煤炭化学研究所 Carbon micron tube/transition metal hydroxide combination electrode material and preparation method thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557026A (en) * 2011-11-09 2012-07-11 南京邮电大学 Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material
CN103253649A (en) * 2013-04-19 2013-08-21 东南大学 Preparation method and application of carbon sponge
CN103950916A (en) * 2014-04-24 2014-07-30 合肥国轩高科动力能源股份公司 Preparation method of carbonaceous anode material for lithium ion batteries
CN104916451A (en) * 2015-05-08 2015-09-16 中国科学院山西煤炭化学研究所 Method for preparing super capacitor electrode material made of nickel oxide nanosheet grown on micro carbon tube
RU2611509C2 (en) * 2015-06-19 2017-02-27 Нина Александровна Попова Method of producing single-layer carbon micro- and nanotubes
CN106744784A (en) * 2015-11-18 2017-05-31 中国海洋大学 A kind of dipping-activation method prepares method of nitrogen oxygen codope Enteromorpha basic unit secondary aperture carbon material and application thereof
CN106744784B (en) * 2015-11-18 2019-03-22 中国海洋大学 A kind of dipping-activation method prepares the method and application thereof of nitrogen oxygen codope Enteromorpha base secondary aperture carbon material
CN105609320A (en) * 2016-03-02 2016-05-25 中国科学院山西煤炭化学研究所 Preparation method for biomass-based hollow carbon microtube/Ni-Co metal sulfide composite electrode material
CN108862235A (en) * 2018-06-07 2018-11-23 上海大学 A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode
CN110002429A (en) * 2019-05-09 2019-07-12 中国科学院山西煤炭化学研究所 Carbon micron tube/transition metal hydroxide combination electrode material and preparation method thereof

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