CN103936987B - Carbon nanotube composite material and preparation method thereof - Google Patents

Carbon nanotube composite material and preparation method thereof Download PDF

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CN103936987B
CN103936987B CN201410191221.1A CN201410191221A CN103936987B CN 103936987 B CN103936987 B CN 103936987B CN 201410191221 A CN201410191221 A CN 201410191221A CN 103936987 B CN103936987 B CN 103936987B
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polyaniline
carbon nano
composite material
preparation
aqueous solution
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CN103936987A (en
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范磊
龚惠芳
郭荣
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Yangzhou University
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Yangzhou University
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Abstract

The invention discloses a carbon nanotube composite material and a preparation method thereof and relates to the technical field of nanomaterial synthesis. The preparation method comprises the following steps: polymerizing ammonium persulfate used as the oxidant and purified multiwalled carbon nanotubes used as a carrier of polyaniline at 0 DEG C ambient temperature to obtain a stable polyaniline/multi-walled carbon nanotubes composite material, and then introducing manganese dioxide under acidic conditions to obtain a manganese dioxide/polyaniline/multi-walled carbon nanotubes composite material. The carbon nanotube composite material is in a tubular structure and polyaniline having particle size of 30-40nm is attached to a tubular body. The electrode made of the multi-walled carbon nanotubes composite material exhibits ideal capacitive properties. The composite material is simple in preparation and has broad application prospect in terms of the super capacitor.

Description

A kind of carbon nano tube compound material and preparation method thereof
Technical field
The present invention relates to the synthesis technical field of nano material.
Background technology
Conducting polymer, can be used as ultracapacitor fake capacitance type electrode because having structure and the physical and chemical performance of uniqueness Material.But its cycle performance is poor, therefore often it is combined with electric double layer type carbon-based material.By integrating both materials Premium properties, carbon nanotube loaded conducting polymer composite material is very big excellent by occupying in new nanotechnology application Gesture.Many research worker report the synthesis technique that CNT and conducting polymer are combined, and the polymer of wherein employing has poly- Pyrroles, polyaniline etc..
At present, in numerous conducting polymers, polyaniline has raw material and is easy to get, and convieniently synthesized, conductivity is high, and uniqueness is mixed The feature of miscellaneous mechanism, has very big development potentiality in conducting high polymers thing field.Due to CNT have higher Electric conductivity, and be combined the easy advantage forming network with polyaniline, will polyaniline be combined with a small amount of CNT it is possible to Significantly increase electric conductivity and the mechanical property of polyaniline.Because polyaniline nano fiber has big specific surface area, Gao Kong Gap rate, it is considered to can improve the low electrochemical electrical conductivity of manganese bioxide electrode material with Polyaniline-modified manganese dioxide, improves dioxy Change the utilization rate of manganese.Meanwhile, stability and the high rate performance of electrode material can be improved.Although polyaniline/manganese dioxide and carbon But the research of nanotube/polyaniline binary composite is it has been reported that for manganese dioxide/polyaniline/multi-walled carbon nano-tubes Trielement composite material preparation and its as electrode material for super capacitor, there is not been reported.
Content of the invention
The present invention provides a kind of method manganese dioxide/polyaniline/multi-walled carbon nano-tubes tri compound easy, with low cost Material.
Manganese dioxide/polyaniline/the multi-wall carbon nano-tube composite material of the present invention has the feature that composite is in pipe Shape structure, the external diameter of body is 20~40 nm, is attached with the polyaniline that particle diameter is 30~40nm on body.
Product can be observed from transmission electron microscope (tem) and there is features above, carbon nano tube surface in-situ preparation one Layer polyaniline particles, that is, polyaniline particles be evenly coated at carbon nano tube surface.
Because CNT has higher electric conductivity, and be combined the easy advantage forming network with polyaniline, will gather Aniline is combined it is possible to significantly increase electric conductivity and the mechanical property of polyaniline with a small amount of CNT.Polyaniline is received Rice fiber has big specific surface area, and high porosity is it is considered to can improve manganese dioxide electrode material with Polyaniline-modified manganese dioxide Material low electric conductivity, manganese dioxide can also improve the specific volume of material.Meanwhile, the stability of electrode material and forthright again can be improved Energy.Prepare manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material electrode and show preferable capacitive properties, this is combined Material is prepared simple and easy to do, has broad application prospects in terms of ultracapacitor.
The present invention also proposes the preparation method of above composite.
Preparation method is: using Ammonium persulfate. as oxidant, using the multi-walled carbon nano-tubes of purification as the carrier of polyaniline, Under 0 DEG C of ambient temperature conditions, polymerization obtains stable polyaniline/multi-wall carbon nano-tube composite material, then draws in acid condition Enter manganese dioxide and obtain manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material.
The present invention is first to remove multi-walled carbon nano-tubes nothing in process of production using the multi-walled carbon nano-tubes purpose of purification Setting carbon and catalyst granules.Present invention process feature has:
(1) with Ammonium persulfate. as oxidant, polyaniline in carbon nano tube surface in-situ preparation and forms uniform clad. Then introduce manganese dioxide in acid condition and obtain manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material.With generally poly- Aniline/multi-wall carbon nano-tube composite material route of synthesis is compared, and has saved preparation reagent, has simplified production craft step.
(2) under 0 DEG C of ambient temperature conditions, polymerization is conducive to improving the molecular weight of polyaniline and obtaining molecular weight distribution relatively Narrow polymer.
(3) the method raw material is easy to get, and product repeatability is high.
The method of specific purification of Multi-wall Carbon Nanotubes is: multi-walled carbon nano-tubes (mwnts) is scattered in hno3Aqueous solution In, after magnetic agitation under conditions of the temperature of mixed system is 120 DEG C, after centrifugation, it is precipitated thing, then through centrifuge washing Colourless to cleaning mixture, then take lower sediment to be vacuum dried purification multi-walled carbon nano-tubes.The present invention adopts liquid phase oxidation CNT is carried out purification, relatively gently it is easy to control, this method greatly reduces sample to the reaction condition of liquid phase oxidation Loss rate.
For scattered solvent hno3The concentration of aqueous solution is 2.6 m.The concentration of nitric acid is bigger, its response speed Bigger, in the unit interval, the weight-loss ratio of CNT is also larger, actually in excessive nitric acid liquid, through time enough, Impurity can be removed, and when concentration of nitric acid is excessive, because response speed is too fast, makes primary response excessively violent, in reactor More brownish red no of middle generation2The concentration that gas, the therefore present invention select nitric acid is 2.6 m so that course of reaction more relaxes.
The concrete grammar preparing polyaniline/multi-walled carbon nano-tubes is: will be dispersed with the hcl water of the multi-walled carbon nano-tubes of purification Add aniline solution in solution, stir under condition of ice bath, obtain mixed solution;Again to mixed solution and dripping mistake Ammonium sulfate, is reacted under stirring condition, is subsequently adding acetone terminating reaction, is taken with deionized water and ethanol centrifuge washing Precipitate, and precipitate is vacuum dried under the conditions of 80 DEG C, grinds, obtain polyaniline/multi-walled carbon nano-tubes.
In addition, for disperse purification the hcl aqueous solution of multi-walled carbon nano-tubes concentration be 1m, during dispersion, purification many Wall carbon nano tube is 0.5g 100ml with the mixing ratio of hcl aqueous solution.Can be effective when acid certain density due to doping Prevention one-dimensional nano structure self assembly ordered arrangement behavior.When adding the hcl of 1m, the polyaniline product of formation will be no The polyaniline nano fiber of rule arrangement, is conducive to compound with CNT.
In described ammonium persulfate aqueous solution, Ammonium persulfate. and the mass ratio that feeds intake of aniline in aniline solution are 11, Deca mistake The speed of ammonium sulfate solution is 1d/3s.Because the hydrophilic of aps, can be dispersed in continuous aqueous phase, polyreaction master Occur in droplet surface.When initiator aps is added with slower speed (3s/ d), the polymerization of the droplet surface of aps in solution Center density is relatively low, now can only form initial polyaniline fiber in a small range, is conducive to polyaniline and CNT Compound.If rate of addition is too fast or aps increases relative to aniline monomer ratio, then can lead to initiator within the unit interval Excessive concentration, causes aniline monomer to assemble formation network structure interior on a large scale, is unfavorable for compound with CNT.
When the mass ratio that feeds intake of aniline in Ammonium persulfate. with aniline solution is 11, the electric conductivity of the composite obtaining Highest.Whole reaction system is carried out in hydrochloric acid medium, and hydrochloric acid provides reaction required acidity, and is entered poly- with dopant form Aniline skeleton, gives its certain electric conductivity.Slowly Deca aps avoids system reaction overheated.Deionized water and washing with alcohol, The inorganic and organic impuritiess of attachment on product can be washed away respectively, water and ethanol have good intersolubility, can wash mutually, Ethanol has good volatility simultaneously.Vacuum condition drying can by washed product when the water that introduces and ethanol remove.
The concrete grammar preparing manganese dioxide/polyaniline/multi-walled carbon nano-tubes is: by polyaniline/multi-walled carbon nano-tubes with After potassium permanganate solution stirring reaction, with deionized water, ethanol centrifuge washing taking precipitate, then dry, grind through 50 DEG C, taking Obtain manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material.Introduce manganese dioxide in acid condition, by potassium permanganate Obtain manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material with the in-situ oxidation reduction reaction of polyaniline.With existing two Manganese oxide/polyaniline composite material route of synthesis is compared, and has saved the reagent of preparation, has simplified production stage.The method is former Material material is easy to get, and product repeatability is high.Manganese dioxide/the polyaniline obtaining/multi-wall carbon nano-tube composite material stability is high, super Level capacitor aspect has broad application prospects.
The concentration of above-mentioned potassium permanganate solution is preferably 0.01~0.06 m.
Because potassium permanganate concentration is larger on the pattern impact of composite.Multiple in fixing polyaniline/multi-walled carbon nano-tubes In the case that condensation material content is 0.05 g, the concentration controlling potassium permanganate solution is 0.01m~0.06 m, the amount of manganese dioxide Increase with the increase of potassium permanganate concentration.When liquor potassic permanganate concentration is less, polyaniline appearance face thickness does not have Substantially increase.When liquor potassic permanganate concentration is 0.02 m~0.04 m it can be seen that one layer two in polyaniline surface distributed Manganese oxide particle, and coating thickness is gradually increased.When liquor potassic permanganate concentration reaches 0.05 m and 0.06 m, not only exist Polyaniline surface covers the thick manganese dioxide particle layer of thick layer, and in polyaniline/multi-wall carbon nano-tube composite material week Enclose the manganese dioxide granule that there is also itself reunion.
Brief description
Fig. 1 is the tem photo of the CNT that purification obtains, and scale is 100 nm.
Fig. 2 is the tem photo of the polyaniline/multi-wall carbon nano-tube composite material preparing, and scale is 100 nm.
Fig. 3 is the tem photo of the manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material preparing, and scale is 100 nm.
Specific embodiment
The term being used in the present invention, unless otherwise specified, typically has those of ordinary skill in the art usual The implication understanding.
With reference to specific embodiment, and with reference to data, the present invention is described in further detail.It should be understood that these enforcements The example present invention solely for the purpose of illustration, rather than limit the scope of the present invention by any way.
Below in an example, the various processes not described in detail and method are conventional methods as known in the art.
Step of preparation process:
1st, the purification of CNT: mwnts is added the hno being 2.6 m equipped with 50 ml concentration3The round bottom of aqueous solution burns In bottle, under the conditions of 120 DEG C, magnetic agitation backflow 24h makes system react completely, after then containing the reaction system centrifugation of precipitation It is precipitated thing, more colourless to cleaning mixture through centrifuge washing, then take lower sediment to be vacuum dried, the many walls carbon obtaining purification is received Mitron.
CNT pattern after purification is as shown in Figure 1.
As seen from Figure 1: the multi-walled carbon nano-tubes of purification is in tubular construction.
2nd, the preparation of polyaniline/multi-wall carbon nano-tube composite material: claim the hcl that 0.5 g CNT adds 100ml 1m 0.5 h is stirred to being uniformly dispersed in aqueous solution.
The above hcl solution container equipped with CNT is placed in ice bath, then adds the benzene containing 2.0g in container Amine monomers solution, 0.5h is to being uniformly dispersed for stirring, then the ammonium persulfate aqueous solution containing 2.0g Ammonium persulfate. is added one with every 3s Speed Deca in above-mentioned mixed system, be then sufficiently stirred for 6h to system reaction completely.
After the completion of reaction, acetone is added to terminate to react.
It is centrifuged successively with deionized water and ethanol and washs clearly three times, then taking precipitate is vacuum dried 24 h at 80 DEG C, Ground again, obtain polyaniline/multi-wall carbon nano-tube composite material.
The pattern of polyaniline/multi-wall carbon nano-tube composite material is also subject to the shadow of aniline monomer and carbon nanotube concentration ratio Ring.While fixing content of carbon nanotubes 2.0 g, change the content (0.5~3.0 g) of aniline monomer, obtain is poly- Aniline/multi-wall carbon nano-tube composite material pattern has certain difference, illustrates between polyaniline and multi-walled carbon nano-tubes mainly Physical absorption.When the content of aniline monomer is 2.0 g, CNT plays template action, and it is as polyaniline nucleation Assemble ground, aniline makes polyaniline cover in carbon nano tube surface than relatively evenly in its superficial growth, and the pattern of formation is preferable.
Composite pattern is as shown in Figure 2.
As can be seen from Fig. 2: be attached to uniform one layer of polyaniline particles in tubulose carbon nano tube surface.
3rd, the preparation of manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material: add 0.05g polyphenyl in conical flask Amine/multi-walled carbon nano-tubes, disposably adds the potassium permanganate solution that concentration is 0.01~0.06m thereto, stirs at room temperature Mix 10 min.Again by eccentric cleaning three times respectively of the solution obtaining deionized water, ethanol, dry in 50 DEG C of thermostatic drying chambers Dry 12 h, more ground, obtain sample.
When the concentration of potassium permanganate solution is 0.03m, obtains manganese dioxide/polyaniline/multi-walled carbon nano-tubes and be combined The pattern of material sample is as shown in Figure 3.
As can be seen from Fig. 3: observed by transmission electron microscope (tem), CNT outer tube diameter is about 20~40 Nm, polyaniline particle diameter is 30~40 nm, and the composite after being polymerized still preferably maintains the tubular structure of CNT.

Claims (5)

1. a kind of preparation method of manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material is it is characterised in that described dioxy Change manganese/polyaniline/multi-wall carbon nano-tube composite material in tubular construction, the external diameter of body is 20~40nm, adheres on body There is the polyaniline that particle diameter is 30~40nm, using Ammonium persulfate. as oxidant, using the multi-walled carbon nano-tubes of purification as polyaniline Carrier, polymerization under 0 DEG C of ambient temperature conditions obtains stable polyaniline/multi-wall carbon nano-tube composite material, then in acidity Under the conditions of introduce manganese dioxide obtain manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material;
Described purification step is: multi-walled carbon nano-tubes is scattered in hno3In aqueous solution, it is 120 DEG C in the temperature of mixed system Under the conditions of after magnetic agitation, be precipitated thing after centrifugation, more colourless to cleaning mixture through centrifuge washing, then take lower sediment true The multi-walled carbon nano-tubes of empty dry purification, described hno3The concentration of aqueous solution is 2.6m;
The preparation process of described manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material is: by polyaniline/multi-wall carbon nano-tube After pipe and potassium permanganate solution stirring reaction, with deionized water, ethanol centrifuge washing taking precipitate, then dry, grind through 50 DEG C Mill, obtains manganese dioxide/polyaniline/multi-wall carbon nano-tube composite material.
2. preparation method according to claim 1 it is characterised in that: the hcl of the multi-walled carbon nano-tubes of purification will be dispersed with Add aniline solution in aqueous solution, stir under condition of ice bath, obtain mixed solution;Again to mixed solution and dripping Ammonium persulfate aqueous solution, is reacted under stirring condition, is subsequently adding acetone terminating reaction, is washed with deionized water and ethanol centrifugation Wash taking precipitate, and precipitate is vacuum dried under the conditions of 80 DEG C, grinds, obtain polyaniline/multi-walled carbon nano-tubes.
3. preparation method according to claim 2 it is characterised in that: the described multi-walled carbon nano-tubes for disperseing purification The concentration of hcl aqueous solution is 1m, and during dispersion, the multi-walled carbon nano-tubes of purification is 0.5g 100ml with the mixing ratio of hcl aqueous solution.
4. preparation method according to claim 2 it is characterised in that: Ammonium persulfate. and benzene in described ammonium persulfate aqueous solution In amine aqueous solution, the mass ratio that feeds intake of aniline is 11, and the speed of Deca ammonium persulfate aqueous solution is 1d/3s.
5. preparation method according to claim 1 it is characterised in that: the concentration of described potassium permanganate solution be 0.01 ~0.06 m.
CN201410191221.1A 2014-05-08 2014-05-08 Carbon nanotube composite material and preparation method thereof Expired - Fee Related CN103936987B (en)

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CN104240967B (en) * 2014-09-26 2017-02-22 东南大学 Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof
CN105244186A (en) * 2015-10-15 2016-01-13 扬州大学 Preparation method of carbon-based ternary complex
CN105778086A (en) * 2016-03-30 2016-07-20 重庆金固特新材料科技有限公司 Method for preparing polyaniline/carbon nanotube conductive composite material through inverse emulsion method
CN105860062A (en) * 2016-05-10 2016-08-17 同济大学 Preparation method of carbon nanotube/polyaniline nanoparticle with negative dielectric constant
CN105860066A (en) * 2016-05-10 2016-08-17 同济大学 Method for preparing carbon nano-tubes/polypyrrole nano-particles with negative dielectric constants
CN106548874A (en) * 2016-11-08 2017-03-29 铜陵市启动电子制造有限责任公司 A kind of addition stannum antimony coats the Static Spinning combination electrode material of manganese dioxide
CN107029703B (en) * 2017-04-29 2019-06-21 扬州大学 Sandwich structure MnOX/C/MnOXThe preparation method of hollow sphere
CN107175107A (en) * 2017-07-03 2017-09-19 扬州大学 The preparation method of yolk eggshell structure Hollow Sphere Composites
CN108490051A (en) * 2018-05-21 2018-09-04 吉林大学 A kind of flexible miniature is from driving gas at normal temperature sensor and preparation method thereof
CN114622105B (en) * 2022-04-08 2023-11-10 内蒙古科技大学 Composite material for extracting niobium and preparation method and application method thereof

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CN102408712B (en) * 2011-09-22 2013-01-23 扬州大学 Polyaniline nanofiber/manganese dioxide nanorod composite material and preparation method thereof

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