CN101235199B - Method for preparing carbon nano-tube modified polyaniline nano fiber composite material - Google Patents
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Abstract
The invention discloses a preparation process of carbon nano-tube modification polyaniline nano fiber conductivity composite material. The characteristics of the invention are that conducting acid treatment for carbon nano-tube with concentrated mixed acid, adding carbon nano-tube which is treated with acid and aniline monomer into perchloric acid water solution according to the weight ratio of 1:6-1-32, and evenly dispersing through ultrasonic processing, using ammonium persulphate as oxidation agent, controlling the molar ratio of ammonium persulphate and aniline monomer within 1:2-1:8, and reacting under the ambient temperature to obtain polyaniline nano fiber/ conductivity composite material of polyaniline coating carbon nano-tube coexisting structure. The process has simple art, and is easy to be controlled. The composite material which is prepared has the characteristics of high electricity conductivity ratio and small influence by system pH valve, large specific surface and excellent electrochemistry property and the like, which is expected to be used on electrode material such as second lithium ion cell and super capacitor and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polyaniline/carbon nano tube compound material, specifically, relate to a kind of preparation method who is applicable to the carbon nano-tube modified polyaniline nano fiber conducing composite material of electrode materials.
Background technology
Polyaniline is cheap and easy to get because of monomer whose, and synthesis technique is simple, the specific conductivity height, and advantages such as the good and electrochemical properties excellence of environmental stability, thereby be considered to have potentiality as aspects such as electrode materials such as lithium ion battery and ultracapacitors.It is not high enough that yet traditional method synthetic polyaniline exists specific storage, and its electroconductibility is subjected to shortcomings such as the influence of environment pH value is big, thereby has limited its practical application.
In recent years, people adopt methods such as template polymerization, no template self-assembly, electrospinning, dilute solution polymerization and interfacial polymerization to prepare micrometer/nanometer structure polyaniline, the polyaniline of nanostructure has than the big and unique characteristics such as nano effect of traditional method synthetic polyaniline specific surface area, and this provides possibility for the electrochemical properties that further improves polyaniline.As reporting among the Chinese patent CN101016412A, adopt the electrochemical properties such as ratio capacitance of the lithium salt doping polyaniline nano-fiber electrode material that processing methodes such as interfacial polymerization, alkali lye dedoping and lithium salt solution mix again make to be far superior to traditional polyaniline electrode material.
Because polyaniline only just can present satisfactory electrical conductivity in the environment of pH value＜4, thus polyaniline to introduce a certain amount of conductive filler material when being used as electrode materials be necessary.Carbon nanotube has particular structure, good electrical conductivity and better chemical stability, and polyaniline and carbon nanotube is compound, and two class materials excellent properties separately is not fully exerted, thereby prepares the matrix material of excellent electricity and chemical property.Relevant preparation electrically conductive polyaniline/carbon nano tube compound material research has become the research focus, and the preparation method mainly comprises: in-situ polymerization [Zengin H, et al., Adv.Mater.Vol.14,1480, (2002); Shi Liyi etc., Chinese patent CN1974667A], solution blending [Qu LW, et al., Macromolecules Vol.37,6055, (2004)], electrochemical polymerization [Chen GZ, et al., Adv.Mater.Vol.12,522, (2000)] etc.Though polyaniline/carbon nano tube compound material that aforesaid method makes has very high specific conductivity, but, cause the chemical property of matrix material to reduce because in this class matrix material, the content of electrochemically inactive material-carbon nanotube is on the high side.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of carbon nano-tube modified polyaniline nano fiber conducing composite material, matrix material with this method preparation, have specific conductivity high and be subjected to system pH influence less, specific surface is big and characteristics such as chemical property excellence, to satisfy the requirement that is used to prepare electrode materialss such as secondary lithium battery and ultracapacitor.
Design of the present invention is as follows:
The invention provides a spot of acid treatment carbon nanotube and a large amount of aniline monomers are placed the high chloro acid solution, with a spot of ammonium persulphate is oxygenant, makes the conducing composite material of polyaniline nano fiber/polyaniline enveloped carbon nanometer tube coexisting structure by chemical oxidising polymerisation.It is acid medium that the present invention selects perchloric acid for use, because ClO
4 -Have bigger size, make the sterically hindered increase of aniline in the oxypolymerization process, thereby reduced the generating rate of polyaniline; Less (the oxygenant: aniline＜1: 2), make the comparatively small amt of the polyaniline fiber " nuclear " of initial formation, reduced initial polyaniline and collided generation accumulative chance mutually of the consumption of oxygenant among the present invention.Above-mentioned two factors will cause the polyaniline of the initial linear structure that generates fully to be grown, and not assemble, thereby can form the polyaniline nano fiber of compound with regular structure.After introducing a spot of acid treatment carbon nanotube, because acid treatment carbon nano tube surface existence-COOH group, can with aniline monomer in-there is hydrogen bond action in the NH group, polymerization takes place in carbon nano tube surface absorption and under the initiator effect and forms the polyaniline enveloped carbon nanometer tube in the small part aniline monomer, and most aniline monomer is assembled the generation polyaniline nano fiber in solution, thereby has formed the matrix material of polyaniline nano fiber/polyaniline enveloped carbon nanometer tube coexisting structure.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of carbon nano-tube modified polyaniline nano fiber conducing composite material is characterized in that, its concrete steps are as follows:
(a) at first adopt dense mixing acid that carbon nanotube is carried out acid treatment, carbon nanotube is put into 98% dense H
2SO
4With 60～70% dense HNO
3(volume ratio: H
2SO
4: HNO
3=3: in the mixing acid 1), the mass ratio of controlling carbon nanotube and mixing acid is 1: 4～20, and heat treated is 6～24 hours under 60 ℃ of temperature, uses the deionized water repetitive scrubbing to neutral then, after the oven dry, makes acid-treated carbon nanotube.
(b), add concentration and be among the high chloro acid solution of 1～3mol/L (consumption of carbon nanotube is 0.5～20g/L high chloro acid solution), ultra-sonic dispersion 1～4 hour with a certain amount of acid treatment carbon nanotube; Again a certain amount of aniline monomer is joined in the above-mentioned mixed system, mixed 0.5～1 hour; High chloro acid solution with ammonium persulphate slowly drips in the above-mentioned solution then, and at room temperature stirring reaction carried out 12～48 hours; At last with product after filtration, attitude carbon nano-tube modified polyaniline nano fiber conducing composite material obtains mixing after the washing, drying.
(c) polymerisate of above-mentioned doping attitude is dispersed in the ammoniacal liquor of 10wt% and carries out stirring reaction 24h, obtain dedoping attitude carbon nano-tube modified polyaniline nano fiber composite material.
Wherein, high chloro acid solution's concentration of ammonium persulphate is to contain 0.05～0.2g ammonium persulphate among every milliliter of high chloro acid solution,
The weight ratio of described acid treatment carbon nanotube and aniline monomer charging capacity is 1: 6～32,
The molar feed ratio of described ammonium persulphate and aniline monomer is 1: 2～8.
Beneficial effect
Compared with prior art, the present invention has following advantage:
(1) simple, control can be mass-produced easily; The matrix material of the carbon nano-tube modified polyaniline nano fiber that (2) makes has the specific conductivity height and is subjected to system pH to influence less, big specific surface and excellent characteristics such as chemical property.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the polyaniline nano fiber of comparative example 1 preparation;
Fig. 2 is the transmission electron microscope photo of the multi-walled carbon nano-tubes modified polyaniline nano-fiber composite material of embodiment 1 preparation;
Fig. 3 is (a) acid treatment carbon nanotube, (b) comparative example 1-polyaniline nano fiber and (c) cyclic voltammetry curve of embodiment 1-multi-walled carbon nano-tubes modified polyaniline nano-fiber composite material: scanning speed=20mV/s, and electrolytic solution is 1mol/L LiPF
6The DMC/EMC/DC mixed solution (1/1/1, w/w).
Embodiment
Below by embodiment the present invention is further elaborated:
Comparative example 1
The aniline monomer of 4.47g (48mmol) is joined among the 1.5mol/L high chloro acid solution of 100mL, mix; Take by weighing 2.75g (12mmol) ammonium persulphate then and be dissolved in the perchloric acid solution of 50mL, ammonium persulfate solution slowly is added drop-wise in the above-mentioned solution, at room temperature stirring reaction carried out 24 hours; With deionized water reaction product is filtered, washed, obtains doped polyaniline after the drying.The polymerisate of above-mentioned doping attitude is dispersed in the ammoniacal liquor of 10wt% and carried out stirring reaction 24 hours, obtain dedoping attitude polyaniline.
The pattern of this polyaniline presents nanometer fibrous structure shown in the transmission electron microscope photo of Fig. 1, the diameter of fiber is about 60～100nm.
Use four point probe technique, the specific conductivity of testing this doped polyaniline nanofiber is 3.5S/cm; The specific conductivity of its dedoping attitude polyaniline nano fiber is very low, only is 3.2 * 10
-9S/cm.
Embodiment 1
A certain amount of multi-walled carbon nano-tubes is put into 98% dense H
2SO
4With 63% dense HNO
3(volume ratio: H
2SO
4: HNO
3=3: in the mixing acid 1), heat treated is 6 hours under 60 ℃ of temperature, uses the deionized water repetitive scrubbing to neutral then, after the oven dry, makes acid-treated multi-walled carbon nano-tubes.Take by weighing 0.14g acid treatment multi-walled carbon nano-tubes and join among the 1.5mol/L high chloro acid solution of 100mL ultra-sonic dispersion 2 hours; Again 4.47g (48mmol) aniline monomer is joined in the above-mentioned mixed system, mixed 0.5 hour.Take by weighing 2.75g (12mmol) ammonium persulphate then and be dissolved among the 1.5mol/L high chloro acid solution of 50mL, ammonium persulfate solution slowly is added drop-wise in the above-mentioned solution, at room temperature stirring reaction carried out 24 hours.With product after filtration, obtain doped polyaniline/multi-wall carbon nano-tube composite material after the washing, drying.The polymerisate of above-mentioned doping attitude is dispersed in the ammoniacal liquor of 10wt% and carries out stirring reaction 24h, obtain dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material.
This multi-walled carbon nano-tubes modified polyaniline matrix material pattern is shown in the transmission electron microscope photo of Fig. 2, and visible matrix material presents the structure of polyaniline nano fiber and the coexistence of polyaniline enveloped carbon nanometer tube.
Use four point probe technique, the specific conductivity of testing this doping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 13.2S/cm; The specific conductivity of its dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 3.0 * 10
-3S/cm is than high 6 orders of magnitude of specific conductivity of the polyaniline nano fiber of the dedoping that adopts comparative example 1 preparation.
Embodiment 2
Repeat the process of embodiment 1, make acid-treated multi-walled carbon nano-tubes.Take by weighing 0.75g acid treatment multi-walled carbon nano-tubes and join among the 1mol/L high chloro acid solution of 50mL ultra-sonic dispersion 4 hours; Again 4.47g (48mmol) aniline monomer is joined in the above-mentioned mixed system, mixed 1 hour.Take by weighing 5.5g (24mmol) ammonium persulphate then and be dissolved in the 1mol/L perchloric acid solution of 50mL, ammonium persulfate solution slowly is added drop-wise in the above-mentioned solution, at room temperature stirring reaction carried out 12 hours.With product after filtration, obtain doped polyaniline/multi-wall carbon nano-tube composite material after the washing, drying.The polymerisate of above-mentioned doping attitude is dispersed in the ammoniacal liquor of 10wt% and carries out stirring reaction 24h, obtain dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material.
Transmission electron microscope photo shows that this multi-walled carbon nano-tubes modified polyaniline matrix material presents the structure of polyaniline nano fiber and the coexistence of polyaniline enveloped carbon nanometer tube.
Use four point probe technique, the specific conductivity of testing this doping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 18.3S/cm; The specific conductivity of its dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 0.45S/cm, than high 8 orders of magnitude of specific conductivity of the polyaniline nano fiber of the dedoping that adopts comparative example 1 preparation.
Repeat the process of embodiment 1, with 69% dense HNO
3Replace 63% dense HNO
3, the treatment time is 24h, makes acid-treated multi-walled carbon nano-tubes.Take by weighing 0.28g acid treatment multi-walled carbon nano-tubes and join among the 3mol/L high chloro acid solution of 100mL ultra-sonic dispersion 1 hour; Again 4.47g (48mmol) aniline monomer is joined in the above-mentioned mixed system, mixed 1 hour.Take by weighing 1.38g (6mmol) ammonium persulphate then and be dissolved in the 3mol/L perchloric acid solution of 30mL, ammonium persulfate solution slowly is added drop-wise in the above-mentioned solution, at room temperature stirring reaction carried out 48 hours.At last with product after filtration, attitude multi-walled carbon nano-tubes modified polyaniline matrix material obtains mixing after the washing, drying.
Transmission electron microscope photo shows that this multi-walled carbon nano-tubes modified polyaniline matrix material presents the structure of polyaniline nano fiber and the coexistence of polyaniline enveloped carbon nanometer tube.
Use four point probe technique, the specific conductivity of testing this doping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 14.8S/cm; The specific conductivity of its dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 0.012S/cm, than high 7 orders of magnitude of specific conductivity of the polyaniline nano fiber of the dedoping that adopts comparative example 1 preparation.
Embodiment 4
Repeat the process of embodiment 1, replace multi-walled carbon nano-tubes with Single Walled Carbon Nanotube, the treatment time is 12h, makes acid-treated Single Walled Carbon Nanotube.Take by weighing 0.28g acid treatment Single Walled Carbon Nanotube and join among the 1.5mol/L high chloro acid solution of 100mL ultra-sonic dispersion 2 hours; Again 4.47g (48mmol) aniline monomer is joined in the above-mentioned mixed system, mixed 0.5 hour.Take by weighing 2.75g (12mmol) ammonium persulphate then and be dissolved in the 1.5mol/L perchloric acid solution of 15mL, ammonium persulfate solution slowly is added drop-wise in the above-mentioned solution, at room temperature stirring reaction carried out 24 hours.At last with product after filtration, attitude multi-walled carbon nano-tubes modified polyaniline matrix material obtains mixing after the washing, drying.
Transmission electron microscope photo shows that this multi-walled carbon nano-tubes modified polyaniline matrix material presents the structure of polyaniline nano fiber and the coexistence of polyaniline enveloped carbon nanometer tube.
Use four point probe technique, the specific conductivity of testing this doping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 16.3S/cm; The specific conductivity of its dedoping attitude multi-walled carbon nano-tubes modified polyaniline matrix material is 0.067S/cm, than high 7 orders of magnitude of specific conductivity of the polyaniline nano fiber of the dedoping that adopts comparative example 1 preparation.
Claims (1)
1. the preparation method of a carbon nano-tube modified polyaniline nano fiber conducing composite material is characterized in that, concrete steps are as follows:
(a) at first adopt dense mixing acid that carbon nanotube is carried out acid treatment, carbon nanotube is put into 98% dense H
2SO
4With 60～70% dense HNO
3Mixing acid in, the mass ratio of controlling carbon nanotube and mixing acid is 1: 4～20, heat treated is 6～24 hours under 60 ℃ of temperature, uses the deionized water repetitive scrubbing to neutral then, after the oven dry, makes acid-treated carbon nanotube;
(b) the acid-treated carbon nanotube that step (a) is made, adding concentration is among the high chloro acid solution of 1～3mol/L, the consumption of carbon nanotube is 0.5～20g/L high chloro acid solution, ultra-sonic dispersion 1～4 hour; Again aniline monomer is joined in the above-mentioned mixed system, mixed 0.5～1 hour; High chloro acid solution with ammonium persulphate slowly drips in the above-mentioned solution then, and at room temperature stirring reaction carried out 12～48 hours; At last with product after filtration, attitude carbon nano-tube modified polyaniline nano fiber conducing composite material obtains mixing after the washing, drying;
(c) with the carbon nano-tube modified polyaniline nano fiber conducing composite material of above-mentioned doping attitude, be dispersed in the ammoniacal liquor of 10wt% and carry out stirring reaction 24h, obtain the carbon nano-tube modified polyaniline nano fiber composite material of dedoping attitude;
Wherein: H in the step (a)
2SO
4: HNO
3Volume ratio be 3: 1,
High chloro acid solution's concentration of ammonium persulphate is to contain 0.05～0.2g ammonium persulphate among every milliliter of high chloro acid solution,
The weight ratio of described acid treatment carbon nanotube and aniline monomer charging capacity is 1: 6～32,
The molar feed ratio of described ammonium persulphate and aniline monomer is 1: 2～8.
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