CN101429336A - Process for producing carbon nano-tube/polyaniline conductive composite material - Google Patents
Process for producing carbon nano-tube/polyaniline conductive composite material Download PDFInfo
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- CN101429336A CN101429336A CNA2008102020220A CN200810202022A CN101429336A CN 101429336 A CN101429336 A CN 101429336A CN A2008102020220 A CNA2008102020220 A CN A2008102020220A CN 200810202022 A CN200810202022 A CN 200810202022A CN 101429336 A CN101429336 A CN 101429336A
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Abstract
The invention discloses a method for preparing a carbon nanometer tube/polyaniline conductive composite material. The method comprises the following steps: (1) )CNTs are weighed, are placed in PECVD, and are subjected to plasma modification; (2) the mixture is put into a flask and is dispersed through water; (3) distilled water and aniline are taken out, are subjected to PH regulation, are poured into the flask and are evenly stirred; (4) under an ice water bath, a (NH4)2S2O8 aqueous solution is dripped to the flask and reacts under high-speed stirring; and (5) the mixture is subjected to vacuum filtration, washing and vacuum drying at the temperature of 80 DEG C to obtain the conductive CNTs/PANI composite material. Through the plasma modification technology, the method improves dispersibility of the CNTs in AN, further has in-situ polymerization with the aniline to obtain the CNTs/PANI composite material of which the conductivity is as high as 2.86S/cm, and has available materials and simple operation.
Description
Technical field
The present invention relates to carbon nanotube (CNTs) is carried out plasma functionalized modification and utilizes carbon nano tube modified to prepare the carbon nano-tube/poly aniline matrix material of electrical property excellence.
Background technology
Carbon nanotube stability is high, conduction, heat conduction and have the intensity of superelevation, is one of up-to-date composite modification agent.The special performance that carbon nano-tube/polymer composite material has, as high thermal conductivity and electric conductivity, visible light/ultraviolet/infrared susceptibility, the attention that makes it produce a large amount of application at aspects such as adjustable electronic instrument, display unit, battery electrode and targeted drug transmission and cause height.Nowadays, existing part scientists is devoted to the preparation and the performance study thereof of carbon nano-tube/poly aniline matrix material, and the method that can be used for preparing carbon nano-tube/poly aniline matrix material has: the two-step approach of the single stage method of electrochemistry and in-situ polymerization, first modification post polymerization.Yet above-mentioned three kinds of preparation methods exist complicated operation, cost height, severe reaction conditions, generation toxic gas, product property and pattern to be difficult to problems such as control in various degree, are difficult to large-scale production.Up to now, do not see the research report for preparing its polyaniline composite material about carbon nanotube and aniline (AN) in-situ polymerization both at home and abroad as yet by plasma modification.Therefore develop a kind of modern design, advanced technology, convenient and simple, with low cost, reaction conditions is gentle, electrical property is excellent, method that can scale production carbon nano-tube/poly aniline matrix material is significant.
Summary of the invention
Technical problem to be solved by this invention is the carbon nano-tube/poly aniline matrix material that gas ions modified carbon nanotube and aniline (AN) in-situ polymerization is prepared the electrical property excellence.
Technical solution of the present invention: a kind of preparation method of carbon nano-tube/poly aniline conducing composite material comprises the following steps:
(1) take by weighing the 0.2g carbon nanotube and place PECVD to carry out the modification processing, the modified technique parameter is: the plasma body source of the gas is an Ar gas, and processing power is 0～100W, treatment time is 0～10min, chamber pressure is 0.04～0.20Torr, and temperature is 20～150 ℃, and electrode distance is 4～12cm;
(2) will join in the round-bottomed flask through the carbon nanotube that step (1) modification is handled, and in the distilled water that wherein adds 50mL, ultra-sonic dispersion 30min;
(3) get 50mL distilled water and 1mL aniline respectively, transfer pH to 1～2 with hydrochloric acid soln, pour in the round-bottomed flask of step (2), high-speed stirring 30min obtains suspension until being uniformly dispersed;
(4) (the NH of dropping and aniline equimolar amount in the suspension of step (3) gained
4)
2S
2O
8Aqueous solution 50mL stirs reaction 2h down in 0～5 ℃ of ice-water bath, obtains solid product;
(5) vacuum filtration step (4) gained solid product, and,, obtain carbon nano-tube/poly aniline conducing composite material again in 80 ℃ of following vacuum-drying 10h with deionized water wash 5 removals unreacted monomer and oligopolymer.
The technique effect of invention: the present invention a kind ofly carries out surface modification by plasma technique to carbon nanotube, further with the method for aniline in-situ polymerization carbon nano-tube/poly aniline matrix material.The principle that the plasma modification method is handled carbon nanotube be energy at plasma treatment procedure ionic medium body particle the energy with chemical bond is suitable usually, and Particle Density and energy are subjected to the constraint (power, pressure and frequency etc.) of external plasma parameter.Therefore, this technology can make various monomer activation form a large amount of free radicals.The existence of this free radical makes carbon nanotube and aniline have better consistency, thereby has improved the dispersiveness of carbon nanotube in the aniline matrix, further with behind the aniline polymerization obtains the carbon nano-tube/poly aniline matrix material of superior electrical property.The key distinction of the two-step approach of the single stage method of this preparation method and in-situ polymerization and electrochemical polymerization, first modification post polymerization is the method for modifying of carbon nano tube surface.For obtaining to coat even, the excellent carbon nano-tube/poly aniline matrix material of electrical property, can adopt the two-step approach of first modification post polymerization, this method can be divided into plasma surface modification and two processes of in-situ polymerization.In the plasma modification process, the number by plasma process parameters controlling carbon nanotube surface formation free radical greatly improves its dispersiveness in the aniline matrix; In the in-situ polymerization process, at suitable polymerizing condition, long polymerization time makes that the surface of carbon nanotube is further coated by more aniline molecule, and along with the polyreaction of carrying out of reaction is finished, the final surface that forms coats uniform carbon nano-tube/poly aniline matrix material.The present invention realizes the surface modification of carbon nanotube by plasma technique, the control plasma process parameters improves the dispersiveness of carbon nanotube in the aniline matrix, select carbon nano tube modified and aniline in-situ polymerization, the carbon nano-tube/poly aniline matrix material of preparation high conductivity.In this preparation system, processing power, treatment time, working pressure that can be by changing plasma body, apply temperature, electrode distance waits the modified effect that improves carbon nanotube, be its dispersiveness in the aniline matrix, obtain pattern and the controlled carbon nano-tube/poly aniline matrix material of conductivity through further in-situ polymerization.Particularly: one, under the Ar action of plasma, the surface forms a large amount of free radicals by carbon nanotube in the present invention, and the control plasma process parameters improves the dispersiveness of carbon nanotube in the aniline matrix; Two, the present invention can prepare that the surface coats evenly, specific conductivity is up to the carbon nano-tube/poly aniline matrix material of 2.86S/cm; Three, the product of the present invention preparation has good electric property and higher thermostability etc.; Four, raw material of the present invention is easy to get, and is simple to operate, and plant and instrument is easy, and superior electrical property, pattern are easily controlled, and it is convenient to handle, and is easy to industrialization, for the control preparation of conductive carbon nanotube based composites provides new approach.
Description of drawings
Fig. 1 is the stereoscan photograph of the product of the embodiment of the invention 1;
Fig. 2 is the infrared spectra of the product of the embodiment of the invention 1;
Fig. 3 is the Raman spectrum of the product of the embodiment of the invention 1.
Embodiment
Below by drawings and Examples the present invention is described in further detail, a kind of plasma modification carbon nanotube and polyaniline composite material thereof comprise the following steps:
(1) takes by weighing the carbon nanotube of 0.2g, and be placed on and carry out modification among the PECVD and handle, the modified technique parameter of setting is: the plasma body source of the gas is an Ar gas, processing power is 0～100W, treatment time is 0～10min, chamber pressure is 0.04～0.20Torr, and temperature is 20～150 ℃, and electrode distance is 4～12cm;
(2) will join in the round-bottomed flask through the carbon nanotube that step (1) modification is handled, and in the distilled water that wherein adds 50mL, ultra-sonic dispersion 30min;
(3) get the distilled water and the aniline of 50mL and 1mL (quality is 1.0219g), transfer pH to 1～2 with hydrochloric acid soln after, pour in the round-bottomed flask of step (2), high-speed stirring 30min is until being uniformly dispersed;
(4) in step (3) gained suspension, drip (NH with the aniline equimolar amount
4)
2S
2O
8(2.5043g 50mL), stirs reaction 2h down in 0～5 ℃ of ice-water bath to the aqueous solution;
(5) vacuum filtration step (4) gained solid product, and with deionized water wash 5 times to remove unreacted monomer and oligopolymer, in 80 ℃ of following vacuum-drying 10h, obtain product of the present invention again.
Further specify the present invention below by embodiment.
Embodiment 1
(1) take by weighing the carbon nanotube of 0.2g, and be placed on and carry out modification among the PECVD and handle, the modified technique parameter of setting is: the plasma body source of the gas is an Ar gas, processing power is 50W, and the treatment time is 5min, and working pressure is 0.10Torr, temperature is 20 ℃, and electrode distance is 12cm;
(2) will join in the round-bottomed flask through the carbon nanotube that step (1) modification is handled, and in the distilled water that wherein adds 50mL, ultra-sonic dispersion 30min;
(3) get the distilled water and the aniline of 50mL and 1mL (quality is 1.0219g), transfer pH to 1.5 with hydrochloric acid soln after, pour in the round-bottomed flask of step (2), high-speed stirring 30min is until being uniformly dispersed;
(4) in step (3) gained suspension, drip (NH with the aniline equimolar amount
4)
2S
2O
8(2.5043g 50mL), stirs reaction 2h down in 5 ℃ of ice-water baths to the aqueous solution;
(5) vacuum filtration step (4) gained solid product, and with deionized water wash 5 times to remove unreacted monomer and oligopolymer, in 80 ℃ of following vacuum-drying 10h, obtain product of the present invention again.
The product that embodiment 1 obtains characterizes the pattern of product, structure, electroconductibility etc. by scanning electronic microscope, infrared spectra, Raman spectrum and four point probe resistivity tester etc.Scanning result shows, the coated with uniform of the carbon nanotube of diameter 20nm one layer thickness be the polyaniline (see figure 1) of 100nm; Infrared and Raman spectrum can obviously be observed the characteristic peak (seeing Fig. 2 and 3) of polyaniline; The specific conductivity that the four point probe resistivity tester records matrix material is 1.44S/cm.
Embodiment 2
In the step (1), discharge power is 0W, and in the step (3), pH is 1.0, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 60nm, and the specific conductivity of gained matrix material is 0.29S/cm.
Embodiment 3
In the step (1), discharge power is 100W, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 100nm, and the specific conductivity of gained matrix material is 1.22S/cm.
Embodiment 4
In the step (1), be 2min discharge time, and in the step (4), the ice-water bath temperature is 0 ℃, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 80nm, and the specific conductivity of gained matrix material is 0.93S/cm.
Embodiment 5
In the step (1), be 15min discharge time, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 120nm, and the specific conductivity of gained matrix material is 1.26S/cm.
Embodiment 6
In the step (1), chamber pressure is 0.04Torr, and in the step (3), pH is 2.0, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 100nm, and the specific conductivity of gained matrix material is 1.14S/cm.
Embodiment 7
In the step (1), chamber pressure is 0.2Torr, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 110nm, and the specific conductivity of gained matrix material is 1.34S/cm.
Embodiment 8
In the step (1), temperature is 150 ℃, and other conditions and step and embodiment 1 are identical, and the polyaniline layer thickness that the carbon tube-surface coats is 120nm, and the specific conductivity of gained matrix material is 1.96S/cm.
Embodiment 9
In the step (1), electrode distance is 4cm, and other conditions and step and embodiment 1 are identical, and the thickness that the carbon tube-surface coats is 130nm, and the specific conductivity of gained matrix material is 2.36S/cm.
Described content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. the preparation method of a carbon nano-tube/poly aniline conducing composite material comprises the following steps:
(1) take by weighing the 0.2g carbon nanotube and place PECVD to carry out the modification processing, the modified technique parameter is: the plasma body source of the gas is an Ar gas, and processing power is 0～100W, treatment time is 0～10min, chamber pressure is 0.04～0.20Torr, and temperature is 20～150 ℃, and electrode distance is 4～12cm;
(2) will join in the round-bottomed flask through the carbon nanotube that step (1) modification is handled, and in the distilled water that wherein adds 50mL, ultra-sonic dispersion 30min;
(3) get 50mL distilled water and 1mL aniline respectively, transfer pH to 1～2 with hydrochloric acid soln, pour in the round-bottomed flask of step (2), high-speed stirring 30min obtains suspension until being uniformly dispersed;
(4) (the NH of dropping and aniline equimolar amount in the suspension of step (3) gained
4)
2S
2O
8Aqueous solution 50mL stirs reaction 2h down in 0～5 ℃ of ice-water bath, obtains solid product;
(5) vacuum filtration step (4) gained solid product, and,, obtain carbon nano-tube/poly aniline conducing composite material again in 80 ℃ of following vacuum-drying 10h with deionized water wash 5 removals unreacted monomer and oligopolymer.
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| CN101830456B (en) * | 2010-05-12 | 2012-01-04 | 中国科学院上海应用物理研究所 | Method for improving electric conductivity of carbon nano tube network |
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| CN105801850A (en) * | 2016-03-30 | 2016-07-27 | 重庆金固特新材料科技有限公司 | Synthesis method of conductive polyaniline and carbon nanotube compound |
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| CN101747667B (en) * | 2010-01-21 | 2012-11-21 | 上海应用技术学院 | Organic carbon nanotube coated with thin polymer film on surface and preparation method thereof |
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| CN106268955B (en) * | 2016-07-19 | 2018-08-14 | 常州大学 | A kind of preparation method of nano-ZnO-conducting polymer composite photo-catalyst |
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