CN101249959A - Carbon/carbon composite nano-tube material having large specific surface area and preparation thereof - Google Patents
Carbon/carbon composite nano-tube material having large specific surface area and preparation thereof Download PDFInfo
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- CN101249959A CN101249959A CNA200810065401XA CN200810065401A CN101249959A CN 101249959 A CN101249959 A CN 101249959A CN A200810065401X A CNA200810065401X A CN A200810065401XA CN 200810065401 A CN200810065401 A CN 200810065401A CN 101249959 A CN101249959 A CN 101249959A
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Abstract
The invention relates to a carbon/carbon composite nanotube material with large specific surface area and a process for preparation thereof, which is structurally characterized in that the material is a hollow tube, and the tube wall is formed by two carbon species with different structures. An inner layer is a graphite laminated structure with a regular structure. An outer layer is a pyrolytic carbon layer which is mainly composed of amorphous carbon and contains certain nano crystalline carbon at the same time. The composite carbon nanotube with the novel structure is mainly prepared by processes of in situ polymerization, carbonization and activation, and has the specific surface area high up to 3000m2/g. The material can be widely applied to fields of carriers of adsorbent and catalyst, energy storage materials, electrode materials and the like.
Description
Technical field
The present invention relates to a kind of carbon/carbon composite nano-tube material and preparation method thereof with bigger serface.The technical field that belongs to the nanometer tube composite materials preparation.
Background technology
Carbon nanotube is a kind of new carbon, and fields such as the carrier of emission on the scene, ultracapacitor, catalyzer, blended material, Chu Qing and environmental protection have extremely wide application prospect (Wang, Q.; Johnson, J.K.J.Chem.Phys.1999,110,577.Du, C.S.; Pan, N.Nanotechnology 2006,17, and 5314).In recent years, carbon nanotube can be by mass preparation (Cassell, A.M.; Raymakers, J.A.; Kong, J.J.Phys.Chem.B 1999,103, and 6484), make the applied research of strengthening carbon nanotube seem very necessary.
Carbon nanotube (CNTs) matrix material with high-specific surface area can be used for the fields such as carrier, energy storage material and electrode materials of nano adsorber, catalyzer, has market application foreground.The specific surface area of carbon nanotube is lower, generally at 100-300m
2(Niu J.J. in the/g scope; Wang J.N.; Jiang Y.; Su L.F.; Ma J.Micro.Meso.Mater.2007,100,1), have document to adopt the method for chemical activation that the specific surface area of carbon nanotube is brought up to 1000m
2More than/the g, reach as high as 1670m
2/ g.
In general, the tube wall degree of graphitization of carbon nanotube is higher, defective is less, and this well-crystallized's carbon species chemically reactive is lower, be difficult to activation, thereby brings very big difficulty for the specific surface area that increases carbon nanotube.If can change the structural pipe wall of carbon nanotube, reduce its degree of graphitization, will help the activation of carbon nanotube, thereby improve its specific surface area (Raymundo-
E.;
P.; Cacciaguerra, T.; Cazorla-Amor ó s, D.; Linares-Solano, A.; B é guin, F.Carbon 2005,43, and 786).Patent of the present invention has prepared a kind of novel carbon nanotube, and its tube wall has double-deck carbon structure: internal layer is well-crystallized's graphite carbon; Skin is mainly amorphous carbon.This carbon nanotube with novel structure can be activated well, can obtain very big specific surface area.
Summary of the invention
The purpose of this invention is to provide a kind of carbon/carbon composite nano-tube material with bigger serface and preparation method thereof, the specific surface area of this matrix material can reach 3000m
2/ g.
Carbon/carbon nano tube compound material provided by the invention is a hollow tube body, and its tube wall is made of two-layer carbon material with different structure: internal layer is for having carbon nanotube; Skin is a pyrolytic carbon layer, and this carbon-coating mainly is made of amorphous carbon, contains the certain amount of nano crystalline carbon simultaneously.
Said carbon nanotube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes in carbon/carbon nano tube compound material provided by the invention, wherein preferred multi-walled carbon nano-tubes.The diameter of carbon nanotube, wall thickness and length are unrestricted.For example, can select external diameter is 30-50nm, and wall thickness is 10-20nm, and length is the carbon nanotube of 0.5-2 μ m.
The preparation method of carbon/carbon composite nano-tube material provided by the invention comprises acidifying, in-situ polymerization, carbonization and four steps of activation:
Acidification technique can strengthen the solubility property of carbon nanotube in solution, its detailed process is: carbon nanotube is mixed with acid solution (as nitric acid), at 20-150 ℃ of following acidifying 0.1-8 hour, solution with water after the acidifying is diluted, then solution is filtered, with deionized water rinse repeatedly, approaching neutral until the pH value.
In position in the polymerization technique, evenly coated one layer of polymeric on the carbon nano tube surface, its thickness can be regulated and control by changing the polymerization technique parameter, and the in-situ polymerization process is: the carbon nanotube after the acidifying is made into the aqueous solution, and the interpolation tensio-active agent, sonic oscillation 0.1-10 hour.Then, be added with organic polymer monomer and acid solution, continued ultrasonic 0.1-5 hour.Slowly drip initiator solution again and carry out home position polymerization reaction, the temperature of control reaction is at 0-80 ℃, and the reaction times is 0.1-15 hour.The ratio of the quality of controlling carbon nanotube, monomer and initiator is a carbon nanotube: monomer: initiator=1: (0.5-80): (5-160).Solution is filtered, consider cake water, ethanol, acetone, N, dinethylformamide equal solvent rinse repeatedly obtains the carbon nanotube of polymer overmold.By the case study on implementation of back as can be seen, in-situ polymerization technology provided by the invention, polymer overmold is even.
Be coated on the polymkeric substance generation carbonization of carbon nano tube surface in the carbonization technique, its process is: the carbon nanotube of polymer overmold is warming up to 500-1200 ℃ with the temperature rise rate of 1-20K/min, stablize 0.5-5 hour after, naturally cool to room temperature.
Activating process is: with the sample after the carbonization according to 1: (0.1-30) mass ratio and activator mix are even, temperature rise rate with 2-30K/min is warming up to 600-1100 ℃, preferred 800-900 ℃, stablized 0.2-4 hour, and naturally cooled to room temperature and obtain required carbon/carbon CNT (carbon nano-tube) matrix material.The result of case study on implementation from behind, activating process can greatly improve the specific surface area of matrix material.
Used acid comprises sulfuric acid, nitric acid, hydrochloric acid or its mixing acid in the said acidization of the present invention.The mixing acid of preferably sulfuric acid and nitric acid.
The said tensio-active agent of the present invention is dialkylamine benzene sulphur sodium, Potassium dodecylbenzenesulfonate, ethylsulfonic acid potassium, isobutyl-sodium sulfonate or hexyl potassium sulfonate.
The said polymer monomer of the present invention is propylene, ethene, V-Pyrol RC, pyrroles, propylene is fine or vinylbenzene.
The said initiator of the present invention is tert-butyl hydroperoxide sodium, ammonium persulphate, lauroyl peroxide, dibenzoyl peroxide, peroxide acetic acid butyl ester or dicumyl peroxide.
The said activator of the present invention is ZnCl
2, H
3PO
4, KOH, NaOH, K
2CO
3Or Na
2CO
3Preferred KOH or NaOH.
Description of drawings
Fig. 1 is the SEM photo of Comparative Examples 1 gained sample of the present invention.
Fig. 2 is the SEM photo of the embodiment of the invention 1 gained sample.
Fig. 3 is the SEM photo of the embodiment of the invention 2 gained samples.
Fig. 4 is the SEM photo of the embodiment of the invention 3 gained samples.
Fig. 5 is the SEM photo of the embodiment of the invention 4 gained samples.
Fig. 6 is the SEM photo of the embodiment of the invention 5 gained samples.
Fig. 7 is the SEM photo of the embodiment of the invention 6 gained samples.
Embodiment
Following case study on implementation will the present invention will be further described.
Implement in the Comparative Examples at each, with the specific surface area of the full-automatic nitrogen absorption of 3H-2000 type specific surface tester working sample.Pattern with HITACHI S-4700 type scanning electron microscope observation sample.
Comparative Examples 1
Carbon nanotube and KOH directly according to 1: 5 mixed, are placed the priming reaction device.Rise to 850 ℃ with 5 ℃/minute temperature rise rates by room temperature, and reacted 2 hours down, obtain sample in 850 ℃.The specific surface area of this sample is: 240m
2/ g.
Embodiment 1:
CNTs is adopted HNO
3In 80 ℃ of acidifyings 4 hours, 300 milligrams of CNTs through acidification of weighing were dissolved in 200 ml waters then, sonic oscillation 2 hours.Add 36 milligrams of Sodium dodecylbenzene sulfonatees, continue vibration 0.5 hour.Add 10 milliliters of fine monomers of propylene and 15 gram ammonium persulphates, control reaction temperature is 25 ℃, reacts after 2 hours, filters.Adopt water, ethanol, acetone to carry out rinse respectively for several times.The gained filter cake was put in 120 ℃ of baking ovens dry 6 hours.Subsequently, sample was carried out carbonizing treatment 3 hours in 850 ℃, gained sample and KOH in 850 ℃ of activation 2 hours, obtain finished product after mixing according to 1: 5 ratio.
Experiment records, and the specific surface area of the sample after the activation is 490m
2/ g.
Embodiment 2:
Preparation process is with embodiment 1, but the consumption of ammonium persulphate is 30 milligrams.Experiment records, and the specific surface area of the sample after the activation is 350m
2/ g.
Embodiment 3:
Preparation process is with embodiment 1, but used polymer monomer is an aniline, and the consumption of ammonium persulphate is 3 milligrams.Experiment records, and the specific surface area of the sample after the activation is 1400m
2/ g.
Enforcement ratio 4:
Preparation process is with embodiment 3, but the consumption of used ammonium persulphate is 6 milligrams.Experiment records, and the specific surface area of the sample after the activation is 2100m
2/ g.
Embodiment 5:
Preparation process is with embodiment 3, but the consumption of used ammonium persulphate is 12 milligrams.Experiment records, and the specific surface area of the sample after the activation is 3000m
2/ g.
Embodiment 6:
Preparation process is with embodiment 3, but the consumption of used ammonium persulphate is 24 milligrams.Experiment records, and the specific surface area of the sample after the activation is 2000m
2/ g.
Claims (6)
1, a kind of carbon/carbon composite nano-tube material, its constitutional features are that this material is a hollow tube body, and its tube wall is made of two-layer carbon material with different structure: internal layer is a carbon nanotube; Skin is a pyrolytic carbon layer, and this carbon-coating contains the certain amount of nano crystalline carbon simultaneously by mainly being made of amorphous carbon.
2, the preparation method of the described carbon/carbon composite nano-tube material of claim 1 is characterized in that this method comprises acidifying, in-situ polymerization, carbonization and four steps of activation.
A. acidifying: use acid solution at 20-150 ℃ of following acidifying 0.1-8 hour carbon nanotube, filter then, wash.
B. in-situ polymerization: the carbon nanotube of acidified processing is made into the aqueous solution, adds tensio-active agent, sonic oscillation 0.1-10 hour.Then, be added with organic polymer monomer and acid solution, continued ultrasonic 0.1-5 hour.Slowly drip initiator solution again and carry out home position polymerization reaction, the temperature of control reaction is at 0-80 ℃, and the reaction times is 0.1-15 hour.The ratio of the quality of controlling carbon nanotube, monomer and initiator is a carbon nanotube: monomer: initiator=1: (0.5-80): (5-160).Solution is filtered, consider cake water, ethanol, acetone, N, dinethylformamide equal solvent rinse repeatedly obtains the carbon nanotube of polymer overmold.
C. carbonization: the carbon nanotube after the polymer overmold is warming up to 500-1200 ℃ with the temperature rise rate of 1-20K/min, stablized 0.5-5 hour.
D. the activation: with the sample after the carbonization according to 1: (0.1-30) mass ratio and activator mix are even, temperature rise rate with 2-30K/min is warming up to 600-1100 ℃, stablized 0.2-4 hour, and naturally cooled to room temperature and obtain required carbon/carbon composite nano carbon tube material.
3, according to the preparation method of claim 2, wherein used acid solution is sulfuric acid, nitric acid, hydrochloric acid or its mixing acid in the acidization.Said carbon CNT (carbon nano-tube) can be single wall nano carbon nanotube or multiple-wall carbon nanotube.
4, according to the preparation method of claim 2, wherein used tensio-active agent is dialkylamine benzene sulphur sodium, Potassium dodecylbenzenesulfonate, ethylsulfonic acid potassium, isobutyl-sodium sulfonate or basic potassium sulfonate in the in-situ polymerization process.
5, according to the preparation method of claim 2, wherein used organic polymer monomer is propylene, ethene, V-Pyrol RC, pyrroles in the in-situ polymerization process, propylene is fine or vinylbenzene.Used initiator is tert-butyl hydroperoxide sodium, ammonium persulphate, lauroyl peroxide, dibenzoyl peroxide, peroxide acetic acid butyl ester or dicumyl peroxide.
6, according to the preparation method of claim 2, wherein used activator is ZnCl in the reactivation process
2, H
3PO
4, KOH, NaOH, K
2CO
3Or Na
2CO
3
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| CN101854128A (en) * | 2009-03-31 | 2010-10-06 | 索尼公司 | Actuator |
| CN101898758A (en) * | 2010-06-29 | 2010-12-01 | 清华大学 | Composite structure of carbon nano tube |
| CN101456554B (en) * | 2009-01-06 | 2011-05-18 | 黑龙江大学 | Method for preparing graphitization nano carbon |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN103769072A (en) * | 2012-10-18 | 2014-05-07 | 湘潭大学 | Titanium dioxide nano-tube-carbon composite material and preparation method and purpose thereof |
| CN103987795A (en) * | 2011-12-08 | 2014-08-13 | 道康宁公司 | Treatment of carbon based filler |
| CN105098185A (en) * | 2014-04-29 | 2015-11-25 | 华为技术有限公司 | Composite cathode material, preparation method thereof, lithium ion secondary battery negative plate and lithium ion secondary battery |
| CN105261487A (en) * | 2015-11-05 | 2016-01-20 | 宁波南车新能源科技有限公司 | Preparation method for nuclear shell porous nano carbon material of super-capacitor electrode |
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| CN111137872A (en) * | 2019-12-24 | 2020-05-12 | 大连理工大学 | Large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder |
| CN111724999A (en) * | 2020-06-18 | 2020-09-29 | 郑州轻工业大学 | Carbon nanotube/activated carbon composite material of core-sheath nano cable structure and preparation method thereof |
| CN113422051A (en) * | 2021-06-15 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof |
| CN113728143A (en) * | 2019-01-06 | 2021-11-30 | 柯利亚·库赛 | Insulating material sandwich wall structure with high carbon content formed by spacing plates |
| CN114772582A (en) * | 2022-04-21 | 2022-07-22 | 南通赛得能源有限公司 | Composite carbon material and application thereof in lithium ion battery |
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| CN101456554B (en) * | 2009-01-06 | 2011-05-18 | 黑龙江大学 | Method for preparing graphitization nano carbon |
| CN101854128B (en) * | 2009-03-31 | 2014-05-28 | 索尼公司 | Actuator |
| CN101854128A (en) * | 2009-03-31 | 2010-10-06 | 索尼公司 | Actuator |
| CN101898758A (en) * | 2010-06-29 | 2010-12-01 | 清华大学 | Composite structure of carbon nano tube |
| CN101898758B (en) * | 2010-06-29 | 2012-08-29 | 清华大学 | Composite structure of carbon nano tube |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN103987795A (en) * | 2011-12-08 | 2014-08-13 | 道康宁公司 | Treatment of carbon based filler |
| CN103769072A (en) * | 2012-10-18 | 2014-05-07 | 湘潭大学 | Titanium dioxide nano-tube-carbon composite material and preparation method and purpose thereof |
| CN103769072B (en) * | 2012-10-18 | 2015-12-16 | 湘潭大学 | Titania nanotube-carbon composite and its production and use |
| CN105098185A (en) * | 2014-04-29 | 2015-11-25 | 华为技术有限公司 | Composite cathode material, preparation method thereof, lithium ion secondary battery negative plate and lithium ion secondary battery |
| US10770720B2 (en) | 2014-04-29 | 2020-09-08 | Huawei Technologies Co., Ltd. | Composite negative electrode material and method for preparing composite negative electrode material, negative electrode plate of lithium ion secondary battery, and lithium ion secondary battery |
| CN105098185B (en) * | 2014-04-29 | 2018-08-14 | 华为技术有限公司 | Composite negative pole material and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
| CN105406076B (en) * | 2014-09-11 | 2019-01-08 | 华为技术有限公司 | A kind of composite negative pole material and its secondary cell |
| CN105406076A (en) * | 2014-09-11 | 2016-03-16 | 华为技术有限公司 | Composite negative electrode material and secondary battery thereof |
| CN105261487A (en) * | 2015-11-05 | 2016-01-20 | 宁波南车新能源科技有限公司 | Preparation method for nuclear shell porous nano carbon material of super-capacitor electrode |
| CN105261487B (en) * | 2015-11-05 | 2016-08-24 | 宁波中车新能源科技有限公司 | Preparation method for the nucleocapsid porous nano material with carbon element of electrode of super capacitor |
| CN113728143A (en) * | 2019-01-06 | 2021-11-30 | 柯利亚·库赛 | Insulating material sandwich wall structure with high carbon content formed by spacing plates |
| CN111137872A (en) * | 2019-12-24 | 2020-05-12 | 大连理工大学 | Large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder |
| CN111724999A (en) * | 2020-06-18 | 2020-09-29 | 郑州轻工业大学 | Carbon nanotube/activated carbon composite material of core-sheath nano cable structure and preparation method thereof |
| CN111724999B (en) * | 2020-06-18 | 2022-11-18 | 郑州轻工业大学 | Carbon nanotube/activated carbon composite material of core-sheath nano cable structure and preparation method thereof |
| CN113422051A (en) * | 2021-06-15 | 2021-09-21 | 杭州职业技术学院 | Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof |
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