CN1283723C - Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use - Google Patents
Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use Download PDFInfo
- Publication number
- CN1283723C CN1283723C CN200410041355.1A CN200410041355A CN1283723C CN 1283723 C CN1283723 C CN 1283723C CN 200410041355 A CN200410041355 A CN 200410041355A CN 1283723 C CN1283723 C CN 1283723C
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- ethylenedioxy thiophene
- tubes
- walled carbon
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims description 53
- 238000002360 preparation method Methods 0.000 title claims description 11
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 9
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 239000002322 conducting polymer Substances 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 230000006698 induction Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000002848 electrochemical method Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
Images
Abstract
The present invention relates to poly-3, 4-ethylenedioxy thiophene/multi-wall carbon nano-tube compound. The present invention is characterized in that the diameter of a carbon nano-tube is from 20 to 40 nanometers, and the length of the carbon nano-tube is from 200 nanometers to 5 micrometers; the diameter of the compound is from 30 to 80 nanometers, and conducting high molecular poly-3, 4-ethylenedioxy thiophene is uniformly covered on the surface of the carbon nano-tube; a quality ratio of a conducting high molecular poly-3, 4-ethylenedioxy thiophene monomer to the multi-wall carbon nano-tube is 1 to 6: 1.The current-voltage response of a capacitor assembled by adopting electrode materials of the poly-3, 4-ethylenedioxy thiophene/multi-wall carbon nano-tube compound of the present invention approaches to that of an ideal capacitor, and the specific capacitance of the capacitor can reach 96 F/g.
Description
One, technical field
The present invention relates to gather-3,4-Ethylenedioxy Thiophene (poly (3,4-ethylenedioxythiophene)), multi-walled carbon nano-tubes and ultracapacitor.
Two, background technology
Follow the sharp increase and the socioeconomic fast development of population, also increasing to the demand of the resource and the energy, and the shortage gradually of the resource and the energy.Based on the energy supply system of oil, coal, owing to when releasing energy, discharge a large amount of pollutents, cause ecotope to go from bad to worse, thereby the mankind will pay attention to clean and reproducible new forms of energy---battery more.Be the atmosphere polluting problem of avoiding the automobile burning oil plant to be brought, adopt battery, obtained in recent years to pay close attention to widely as automobile power.But automobile power cell is more and more higher to the requirement of power density, has surpassed current battery technology developmental level.Ultracapacitor (being called electrochemical capacitor again) has special advantages aspect power characteristic.Their energy density approximately is 20～30% of a lead-acid cell, but its power density is big, can be used as the output pulses energy, can be big electric current is instantaneous discharges and recharges.In electromobile, they can be used as the power accessory power supply of vehicle when startup, acceleration, climbing; When brake, as the important devices of recovered energy.So, ultracapacitor and battery combination can prevent when using the luxus consumption of battery and deterioration [referring to (a) Zhu Lei, Wu Bairong, Chen Hui, Liu Mingyi, simple rising sun space, Li Zhiqiang, rare metal, the 27th the 3rd phase of volume, 385-390; (b) S.Nomoto, H.Nakata, K.Yoshioka, A.Yoshida, H.Yoneda, J.Power Sources, 97-98 (2001) 807-811; (c) A.K.Shukla, A.S.Arico, V.Antonucci, Renewable and Sustainable Energy Reviews, 5 (2001) 137-155].
Poly--3, the 4-Ethylenedioxy Thiophene is a kind of thiophene series conductive polymers derivative, be characterized in that chemical property is stable, electrochemical reaction is rapid, preparation applies to ultracapacitor field, field of biosensors and organic light-emitting device field easily widely [referring to (a) Johan Bobacka, Anal.Chem.1999,71,4932-4937; (b) Xinyan Cui, David C.Martin, Sensors and Actuators B 89 (2003) 92-102; (c) Soumyadeb Ghosh, Olle Inganas, Adv.Mater 1,999 11 No.14 1214-1218].Mutually tangle between the carbon nanotube and form a kind of structure of macropore, not only can reduce the resistance that electrolyte ion shuttles back and forth therein, and make electrostatic double layer discharge and recharge acceleration [referring to (a) Chatterjee, AK; Sharon, M; Baneriee, R; Neumann-Spallart, M, Electrochim.Acta 48 (23) (2003) 3439-34453; (b) Frackowiak, E; Beguin, F, Carbon 40 (2002) 1775-17875; (c) Frackowiak, K.Jurewicz, S.Delpeux, F.Beguin, J.Power sources, 97-98 (2001) 822-825], thereby itself just can be used as electrode materials the carbon mitron.Yet the specific surface area of purified carbon nanotube is little, and (Single Walled Carbon Nanotube BET specific surface area is generally less than 200m
2/ g, many walls are less than 100m
2/ g), be generally less than 40F/g than electric capacity.In order to improve the ratio electric capacity of carbon nanotube, take this dual mode usually: carbon nanotube is activated or carbon nanotube is formed mixture as the carrier of other material.The means of activated carbon nano-tube are such as hot acid treatment [Li, CS; Wang, DZ; Wu, JJ; Lu, WZ; Liang, J; J.Inorg.Mater.18 (5) (2003) 1010-1016], CO
2Oxidation [Li, CS; Wang, DZ; Liang, TX; Li, GT; Wang, XF; Cao, MS; Liang, J; Sci.China Ser.E-Technol Sci.46 (4) (2003) 349-354], KOH activation [referring to Frackowiak, E; Delpeux, S; Jurewicz, K; Szostak, K; Cazorla-Amoros, D; Beguin, F, Chem.Phys.Lett.361 (2002) 35-41] etc.; The mixture coupling mainly is utilize carbon nanotube loose porous, the character of stable conduction, with other type, more higher than capacity ratio, but poorly conductive or be not easy to form loose porous material (gac, metal oxide, conducting polymer etc.) load to above the carbon nanotube, such as, people such as Yng-ke Zhou [referring to Zhou, YK; He, BL; Zhou, WJ; Huang, J; Li, XH; Wu, B; Li, HL, Electrochim.Acta, 49 (2) (2004) 257-262] and people such as Tao Liu [referring to Tao Liu, T.V.Sreekumar, Satish Kumar, Robert H.Hauge, Richard E.Smalley, Carbon 41 (2003) 2427-2451] Single Walled Carbon Nanotube and polyaniline is compound, be used to make ultracapacitor; People such as Girish Arabale are [referring to Girish Arabale, Deepali Wagh, Mahesh Kulkami, I.S.Mulla, S.P.Vemekar, K.Vijayamohanan, A.M.Rao, Chem.Phys.Lett.376 (2003) 207-213] ruthenium oxide of carbon nanotube and incorporeity is compound, be used for electrical condenser; People such as Xiao-feng Wang [referring to (a) Wang, XF; Wang, DZ; Liang, L; J.Inorg.Mater.8 (2) (2003) 331-3368, (b) Wang, XF; Wang, DZ; Liang, J; Chin.J.Inorg.Chem.9 (2) (2003) 137-141] also studied carbon nanotube-nickel oxide mixture as super capacitor material; People such as Qiangfeng Xiao [referring to Xiao, QF; Zhou, X; Electrochim.Acta 48 (5) (2003) 575-5809] studied multi-walled carbon nano-tubes and polythiophene derivant composite materials; People such as E.Frackowiak [referring to (a) E.Frackowiak, K.Jurewicz, K.Szostak, S.Delpeux, F.Beguin, FuelProcessing Technology 77-78 (2002) 213-219; (b) Frackowiak, K.Jurewicz, S.Delpeux, F.Beguin, J.Power sources, 97-98 (2001) 822-825], and people such as K.Jurewicz [referring to K.Jurewicz, S.Delpeux, V.Bertagna, F.Beguin, E.Frackowiak, Chem.Phys.Lett.347 (2001) 36-40] then studied carbon nanotube-Pt/Polypyrrole composite material.But do not see as yet poly--3, the report of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.
Three, summary of the invention
The purpose of this invention is to provide a kind of poly--3, the application in the preparation ultracapacitor of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture and preparation method thereof and mixture.
Technical scheme of the present invention is as follows:
A kind of poly--3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture, wherein the diameter of carbon nanotube is the 20-40 nanometer, length is 200 nanometers-5 micron, the diameter of mixture is the 30-80 nanometer, and conducting polymer gathers-3, and the 4-Ethylenedioxy Thiophene covers carbon nano tube surface equably, conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 1～6.8: 1.
In the above-mentioned mixture, gather-3, the 4-Ethylenedioxy Thiophene has crystalline structure, belongs to rhombic system, and lattice constant is: a=14.0 , b=6.8 , c=7.8 .
A kind of preparation method of above-mentioned mixture, it is that A is restrained multi-walled carbon nano-tubes, (0.7～4.2) A gram p-methyl benzenesulfonic acid (CH
3C
6H
4SO
3H) and (12.0～86.0) A gram Iron(III) chloride hexahydrate (FeCl
36H
2O) mix, in its adding (40～240) A ml distilled water, with ultrasonic 30 minutes (ultrasonic frequency 20KHz of ultrasonoscope, power 800W), then, under room temperature, stirring, drip (1.0～6.0) A gram 3,4-Ethylenedioxy Thiophene monomer, after dropwising, continue to stir 36 hours, after polymerization finishes, to gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture leaches, and cleans with distilled water repeatedly, up to using AgNO
3Can not check that the washings that filters out has Cl
-Ion, drying promptly gets and gathers-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.In order to make monomer polymerization complete, during reaction, oxygenant (FeCl
36H
2O) and the mol ratio of monomer (3, the 4-Ethylenedioxy Thiophene) kept approximately 7: 1.
Of the present invention poly--3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture is through XRD determining, and the result shows and load on poly--3 on the carbon nanotube that the 4-Ethylenedioxy Thiophene has orthohormbic structure.The position at peak and intensity all are complementary with literature value [referring to (a) K.E.Aasmundtveit, E.J.Sainuelsen, L.A.A.Pettersson, O.Inganas, T.Johansson, R.Feidenhans, Synth.Met.101 (1999) 561-564; (b) Li Niu, CaritaKvarnstrom, K.Froberg, Ari Ivaska, Synth.Met.122 (2001) 425-429; (c) K.E.Aasmundtveit, E.J.Sainuelsen, O.Inganas, L.A.A.Pettersson, T.Johansson, S.Ferrer, Syth.Met.113 (2000) 93-97].Analyze by TEM photo and SEM photo, observe of the present invention poly-ly-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture diameter is 30-80nm, and length is the 0.5-5 micron.
The model capacitor fabrication that applies to electrochemical measurement is as follows: a certain amount of electrode materials and graphitized carbon black, polytetrafluoroethylene (PTFE) emulsion mixed grinding is even, infrared lamp is oven dry down, then under the pressure of 400PSI, be pressed into the disk that quality equates, as two electrodes of electrical condenser, card is to collector respectively.Shield retaining is a glass fibre, and electrolytic solution is 1M H
2SO
4
Test shows, with of the present invention poly--3, the model ultracapacitor that 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture is made as electrode materials has typical capacitor specific characteristics, the electrode materials electrochemical properties is stable, the ratio electric capacity of composite electrode material is greater than simple multi-walled carbon nano-tubes, also gather-3, the 4-Ethylenedioxy Thiophene greater than simple.
Four, description of drawings
Fig. 1 is of the present invention poly--3, the XRD figure of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture, and wherein simple carbon nanotube and simple poly--3, the 4-Ethylenedioxy Thiophene is also listed as reference.A is the XRD figure of simple multi-walled carbon nano-tubes among the figure, and b gathers-3 merely, 4-Ethylenedioxy Thiophene XRD figure, and c is the XRD figure of mixture.
Fig. 2 is of the present invention poly--3, the SEM photo of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.A is the SEM figure of simple multi-walled carbon nano-tubes among the figure, and b gathers-3 merely, 4-Ethylenedioxy Thiophene SEM figure, and c is the SEM figure of mixture.
Fig. 3 is of the present invention poly--3, the TEM photo of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.Among the figure, a is the simple TEM figure that keeps away carbon nanotube more, and b is the TEM figure (owing to gather-3 merely, the 4-Ethylenedioxy Thiophene can't be scattered in water or the ethanol, can't directly obtain TEM figure) of mixture.
Fig. 4 adopts mixture (PEDOT: MWNT=1: 1) electrical condenser " cyclic voltammetric " figure under different voltage scan rate of assembling of electrode materials.Electric current-voltage responsive is near ideal capacitor.
Fig. 5 is that the continuous current of electrical condenser under different electric currents of being assembled fills-discharge curve, and charging curve and discharge curve be symmetry substantially, and electrode for capacitors reaction reversibility is good.
Five, embodiment
Embodiment 1. gathers-3, the preparation of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture (conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 6.8: 1).
Adding diameter in the 100mL beaker is the multi-walled carbon nano-tubes 0.15g of 20-40 nanometer, p-methyl benzenesulfonic acid 0.46g, Iron(III) chloride hexahydrate 13.1g and 40mL distilled water.Above-mentioned beaker placed ultrasonic washing instrument 30 minutes.Fully the dissolving back dropwise drips 3 in room temperature, 4-Ethylenedioxy Thiophene monomer 1.02g under the situation of induction stirring.Room temperature induction stirring reaction 36 hours.Product filters, and leaches mixture, cleans with distilled water repeatedly, up to using AgNO
3Filtrate is can not check in aqueous solution inspection Cl
-Ion.Infrared lamp is oven dry down, promptly get of the present inventionly to gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.
Embodiment 2. gathers-3, the preparation of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture (conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 68: 1)
Adding diameter in the 100mL beaker is the multi-walled carbon nano-tubes 0.015g of 20-40 nanometer, p-methyl benzenesulfonic acid 0.46g, Iron(III) chloride hexahydrate 13.0g and 40mL distilled water.Above-mentioned beaker placed ultrasonic washing instrument 30 minutes.Fully the dissolving back dropwise drips 3 in room temperature, 4-Ethylenedioxy Thiophene monomer 1.02g under the situation of induction stirring.Room temperature induction stirring reaction 36 hours.Product filters, and leaches mixture, cleans with distilled water repeatedly, up to using AgNO
3Filtrate is can not check in aqueous solution inspection Cl
-Ion.Infrared lamp is oven dry down, promptly get of the present inventionly to gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.Present embodiment poly--3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture is used to prepare ultracapacitor, and performance is not good.
Embodiment 3. gathers-3, the preparation of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture (conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 3: 1)
Adding diameter in the 100mL beaker is the multi-walled carbon nano-tubes 0.20g of 20-40 nanometer, p-methyl benzenesulfonic acid 0.28g, Iron(III) chloride hexahydrate 8.0g and 40mL distilled water.Above-mentioned beaker placed ultrasonic washing instrument 30 minutes.Fully the dissolving back dropwise drips 3 in room temperature, 4-Ethylenedioxy Thiophene monomer 0.6g under the situation of induction stirring.Room temperature induction stirring reaction 36 hours.Product filters, and leaches mixture, cleans with distilled water repeatedly, up to using AgNO
3Filtrate is can not check in aqueous solution inspection Cl
-Ion.Infrared lamp is oven dry down, promptly get of the present inventionly to gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.
Embodiment 4. gathers-3, the preparation of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture (conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 1: 1)
Adding diameter in the 100mL beaker is the multi-walled carbon nano-tubes 0.20g of 20-40 nanometer, p-methyl benzenesulfonic acid 0.10g, Iron(III) chloride hexahydrate 2.7g and 40mL distilled water.Above-mentioned beaker placed ultrasonic washing instrument 30 minutes.Fully the dissolving back dropwise drips 3 in room temperature, 4-Ethylenedioxy Thiophene monomer 0.2g under the situation of induction stirring.Room temperature induction stirring reaction 36 hours.Product filters, and leaches mixture, cleans with distilled water repeatedly, up to using AgNO
3Filtrate is can not check in aqueous solution inspection Cl
-Ion.Infrared lamp is oven dry down, promptly get of the present inventionly to gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.
Embodiment 5. gathers-3, and 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture applies to ultracapacitor.
The model capacitor fabrication that embodiment 1 resulting mixture is applied to electrochemical measurement is as follows: a certain amount of composite electrode material and graphitized carbon black, polytetrafluoroethylene (PTFE) emulsion are pressed 8: 1: 1 mixed, grind evenly, infrared lamp is oven dry down, then under the pressure of 400PSI, be pressed into the disk that quality equates, as two electrodes of electrical condenser, be attached on the collector respectively.Shield retaining is a glass fibre, and electrolytic solution is 1M H
2SO
4Measurement is calculated through circulation execution peace, is 96F/g than electric capacity.This greater than simple multi-walled carbon nano-tubes (15F/g), also gathers-3,4-Ethylenedioxy Thiophene (80F/g) greater than simple than electric capacity.
Embodiment 6. gathers-3, and 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture applies to ultracapacitor.
The model capacitor fabrication that embodiment 2 resulting mixtures is applied to electrochemical measurement is as follows: a certain amount of electrode materials and graphitized carbon black, polytetrafluoroethylene (PTFE) emulsion are pressed 8: 1: 1 mixed, grind evenly, infrared lamp is oven dry down, then under the pressure of 400PSI, be pressed into the disk that quality equates, as two electrodes of electrical condenser, be attached on the collector respectively.Shield retaining is a glass fibre, and electrolytic solution is 1M H
2SO
4Measuring calculating through cyclic voltammetry, is 90F/g than electric capacity.This greater than simple multi-walled carbon nano-tubes (15F/g), also gathers-3,4-Ethylenedioxy Thiophene (80F/g) greater than simple than electric capacity.
Embodiment 7. gathers-3, and 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture applies to ultracapacitor
The model capacitor fabrication that embodiment 3 resulting mixtures is applied to electrochemical measurement is as follows: a certain amount of electrode materials is mixed in 8: 1: 1 ratios with graphitized carbon black, polytetrafluoroethylene (PTFE) emulsion, grind evenly, infrared lamp is oven dry down, then under the pressure of 400PSI, be pressed into the disk that quality equates, as two electrodes of electrical condenser, be attached on the collector respectively.Shield retaining is a glass fibre, and electrolytic solution is 1M H
2SO
4Measuring calculating through cyclic voltammetry, is 58F/g than electric capacity.This than electric capacity greater than simple multi-walled carbon nano-tubes (15F/g).
Embodiment 8. gathers-3, and 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture applies to ultracapacitor.
The model capacitor fabrication that embodiment 4 resulting mixtures is applied to electrochemical measurement is as follows: a certain amount of electrode materials is mixed in 8: 1: 1 ratios with graphitized carbon black, polytetrafluoroethylene (PTFE) emulsion, grind evenly, infrared lamp is oven dry down, then under the pressure of 400PSI, be pressed into the disk that quality equates, as two electrodes of electrical condenser, be attached on the collector respectively.Shield retaining is a glass fibre, and electrolytic solution is 1M H
2SO
4Measuring calculating through cyclic voltammetry, is 42F/g than electric capacity.This than electric capacity greater than simple multi-walled carbon nano-tubes (15F/g).
Claims (4)
1. one kind poly--3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture, it is characterized in that: wherein the diameter of carbon nanotube is the 20-40 nanometer, length is 200 nanometers-5 micron, the diameter of mixture is the 30-80 nanometer, and conducting polymer gathers-3, and the 4-Ethylenedioxy Thiophene covers carbon nano tube surface equably, conducting polymer gathers-3, and the mass ratio of 4-Ethylenedioxy Thiophene and multi-walled carbon nano-tubes is 1～6.8: 1.
2. according to the described mixture of claim 1, it is characterized in that: gather-3, the 4-Ethylenedioxy Thiophene has crystalline structure, belongs to rhombic system.
3. the preparation method of the described mixture of claim 1, it is characterized in that: A is restrained multi-walled carbon nano-tubes, (0.7～4.2) A gram p-methyl benzenesulfonic acid and (12.0～86.0) A gram Iron(III) chloride hexahydrate mix, in its adding (40～240) A ml distilled water, with frequency 20KHz ultrasonic wave effect 30 minutes, then, in room temperature, stir and drip (1.0～6.0) A gram 3 down, 4-Ethylenedioxy Thiophene monomer is after dropwising, continue to stir 36 hours, after polymerization finishes, will gather-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture leaches, clean with distilled water repeatedly, up to using AgNO
3Can not check that the washings that filters out has Cl
-Ion, drying promptly gets and gathers-3,4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture.
4. claim 1 is described gathers-3, the application of 4-Ethylenedioxy Thiophene/multi-walled carbon nano-tubes mixture in the preparation ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041355.1A CN1283723C (en) | 2004-07-13 | 2004-07-13 | Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041355.1A CN1283723C (en) | 2004-07-13 | 2004-07-13 | Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594433A CN1594433A (en) | 2005-03-16 |
| CN1283723C true CN1283723C (en) | 2006-11-08 |
Family
ID=34665003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410041355.1A Expired - Fee Related CN1283723C (en) | 2004-07-13 | 2004-07-13 | Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1283723C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060291142A1 (en) * | 2004-12-13 | 2006-12-28 | Ohio State University Research Foundation | Composite material containing nanotubes and an electrically conductive polymer |
| CN1300259C (en) * | 2005-04-20 | 2007-02-14 | 天津大学 | Method for preparing nonlinear optical material of linkage nano carbon tubes of polythiophene methylene |
| JP5771873B2 (en) | 2006-05-04 | 2015-09-02 | エルジー・ケム・リミテッド | High-capacity / high-power electrochemical energy storage element using conductive (conductive) polymer composite |
| CN100441634C (en) * | 2006-12-26 | 2008-12-10 | 西安交通大学 | Preparation method of conductive high polymer and carbon nanotube composite electrode material |
| CN100441638C (en) * | 2006-12-26 | 2008-12-10 | 西安交通大学 | Method for preparing composite electrode material for super capacitor |
| CN101186745B (en) * | 2007-11-09 | 2011-06-08 | 华南理工大学 | Method for preparing polythiophene-metal oxide nano composite material |
| CN102025018A (en) * | 2009-09-17 | 2011-04-20 | 深圳富泰宏精密工业有限公司 | Antenna and wireless communication device using same |
| CN109293934B (en) * | 2018-09-03 | 2021-02-26 | 重庆工业职业技术学院 | Preparation method of polythiophene liquid crystal/multi-walled carbon nanotube composite material |
| CN110336025B (en) * | 2019-06-28 | 2021-04-27 | 安徽清泉新能源科技集团有限责任公司 | Lithium-sulfur battery positive electrode material and preparation method thereof |
-
2004
- 2004-07-13 CN CN200410041355.1A patent/CN1283723C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1594433A (en) | 2005-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | High energy density and low self-discharge of a quasi-solid-state supercapacitor with carbon nanotubes incorporated redox-active ionic liquid-based gel polymer electrolyte | |
| Liang et al. | Toward fiber-, paper-, and foam-based flexible solid-state supercapacitors: electrode materials and device designs | |
| Arthisree et al. | Optically active polymer nanocomposite composed of polyaniline, polyacrylonitrile and green-synthesized graphene quantum dot for supercapacitor application | |
| Ma et al. | Electrospun lignin-derived carbon nanofiber mats surface-decorated with MnO2 nanowhiskers as binder-free supercapacitor electrodes with high performance | |
| Yu et al. | Polypyrrole-anchored cattail biomass-derived carbon aerogels for high performance binder-free supercapacitors | |
| Wu et al. | Synthesis and characterization of hierarchical Bi2MoO6/Polyaniline nanocomposite for all-solid-state asymmetric supercapacitor | |
| Xiang et al. | High electrochemical performance of RuO2–Fe2O3 nanoparticles embedded ordered mesoporous carbon as a supercapacitor electrode material | |
| Chen et al. | Design and synthesis of hierarchical nanowire composites for electrochemical energy storage | |
| Sharma et al. | Multiwall carbon nanotube supported poly (3, 4-ethylenedioxythiophene)/manganese oxide nano-composite electrode for super-capacitors | |
| Ding et al. | An investigation of spinel NiCo2O4 as anode for Na-ion capacitors | |
| Sen et al. | Electrochemical performances of poly (3, 4-ethylenedioxythiophene)–NiFe2O4 nanocomposite as electrode for supercapacitor | |
| CN101527202B (en) | Oxidized grapheme/polyaniline super capacitor composite electrode material and preparation method | |
| Zhu et al. | Oxidation-etching preparation of MnO2 tubular nanostructures for high-performance supercapacitors | |
| Song et al. | Freestanding needle-like polyaniline–coal based carbon nanofibers composites for flexible supercapacitor | |
| Zhang et al. | Development of redox deposition of birnessite-type MnO2 on activated carbon as high-performance electrode for hybrid supercapacitors | |
| Vijeth et al. | Flexible and high energy density solid-state asymmetric supercapacitor based on polythiophene nanocomposites and charcoal | |
| He et al. | Mosaic-structured SnO2@ C porous microspheres for high-performance supercapacitor electrode materials | |
| Zhou et al. | High-performance pseudocapacitors from kraft lignin modified active carbon | |
| Huang et al. | Synthesis and application of MnO2/PANI/MWCNT ternary nanocomposite as an electrode material for supercapacitors | |
| CN107201573A (en) | A kind of preparation method and applications of cobalt disulfide and carbon nano-fiber composite material | |
| CN1283723C (en) | Poly-3,4-ethylenedioxy thiophene/multi-wall carbon nanotube compositions and their preparation process and use | |
| Ran et al. | Nano vanadium nitride incorporated onto interconnected porous carbon via the method of surface-initiated electrochemical mediated ATRP and heat-treatment approach for supercapacitors | |
| Liu et al. | Preparation of stable composite porous nanofibers carried SnOx-ZnO as a flexible supercapacitor material with excellent electrochemical and cycling performance | |
| Zheng et al. | Synthesis of hierarchical reduced graphene oxide/SnO2/polypyrrole ternary composites with high electrochemical performance | |
| Su et al. | Flexible two-ply yarn supercapacitors based on carbon nanotube/stainless steel core spun yarns decorated with Co3O4 nanoparticles and MnOx composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jianghai Capacitor Co., Ltd., Nantong Assignor: Nanjing University Contract fulfillment period: 2007.4.15 to 2013.4.15 contract change Contract record no.: 2008320000177 Denomination of invention: Collagen modified poly(3-hydroxybutyrate-3-hydroxyvalerate) and its preparing method and application Granted publication date: 20061108 License type: Exclusive license Record date: 2008.9.22 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.4.15 TO 2013.4.15 Name of requester: NANTONG JIANGHAI CAPACITOR CO. Effective date: 20080922 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061108 Termination date: 20110713 |