CN101307134A - P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use - Google Patents
P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use Download PDFInfo
- Publication number
- CN101307134A CN101307134A CNA2008101243132A CN200810124313A CN101307134A CN 101307134 A CN101307134 A CN 101307134A CN A2008101243132 A CNA2008101243132 A CN A2008101243132A CN 200810124313 A CN200810124313 A CN 200810124313A CN 101307134 A CN101307134 A CN 101307134A
- Authority
- CN
- China
- Prior art keywords
- poly
- ethene dioxythiophene
- preparation
- electrode
- methyl
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims description 26
- 241000790917 Dioxys <bee> Species 0.000 title 1
- 239000005977 Ethylene Substances 0.000 title 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title 1
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 13
- 239000002608 ionic liquid Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000002848 electrochemical method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
Abstract
The invention relates to poly (3, 4-ethylenedioxy thiophene) conductive polymer, which is p-type doped polymer prepared by electropolymerization of 3, 4-ethylenedioxy thiophene monomer, adoption of 1-methyl-3-butyl imidazole tetrafluoborate as electrolyte and dopant, and utilization of the potentiostatic method. The structure of the poly (3, 4-ethylenedioxy thiophene) conductive polymer is a porous structure the surface of which is formed by accumulation of a plurality of particles between 800 nanometers and about 2 micrometer. The specific capacitance of the poly (3, 4-ethylenedioxy thiophene) conductive polymer reaches 113 to 158 F/g, and the cyclical stability can reach 70000 times. The invention discloses a method for manufacturing the same.
Description
Technical field
The present invention relates to gather (3, the 4-ethene dioxythiophene) and its synthetic method and its application in electrode material for super capacitor.
Background technology
Follow the sharp increase and the socioeconomic fast development of population, the shortage gradually of the resource and the energy, ecotope goes from bad to worse, and the mankind will rely on clean and reproducible new forms of energy more.More and more higher in many energy storage device application facet in recent years to the requirement of power density, surpassed the standard design ability of present level battery.Generally cost is low except that requiring, the life-span long, more wish to have higher unit weight or energy density of unit volume (Wh/kg) or maximum power density (W/kg).(electrochemical capacitor, EC), particularly (supercapacitors ultracapacitors), has special advantages to ultracapacitor to electrochemical capacitor aspect power characteristic.Although their energy density is lower than rechargeable battery, but its power density is big, can be used as the output pulses energy, can be big electric current is instantaneous discharges and recharges, the important devices of recovered energy when improving power and brake when in electromobile, can be used as startup, acceleration, the climbing of vehicle; Can prevent when using with battery combination 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-ethene dioxythiophene) are a kind of thiophene series conductive polymers derivatives, are characterized in synthetic simple, stable in properties, and bandwidth is narrow, the electroconductibility height, processing easily, environmental sounds etc. have caused great attention.The good character of this material can be used for anti-electrostatic and applies, biosensor, and photodiode, secondary cell, electric chemical super capacitor, and field such as molecular circuit [referring to (a) Johan Bobacka, Anal.Chem.71 (1999), 4932-4937; (b) Xinyan Cui, David C.Martin, Sensors and Actuators B 89 (2003), 92-102; (c) Soumyadeb Ghosh, Olle Inganas, Adv.Mater.11 (1999), 1214-1218].
The synthetic method of conducting polymer has methodology of organic synthesis and electrochemical method for synthesizing usually.Wherein, organic synthesis side often obtains the neutral conducting polymer.Generally, the electric conductivity of the conducting polymer of undoped is positioned at semi-conductive scope, and through overdoping, its specific conductivity can increase substantially; And electrochemical method for synthesizing often obtains is adulterated conducting polymer.The electrochemical polymerization conductive polymers can carry out in organic system, also can carry out in water solution system [referring to (a) V.
H.Randriamahazaka, C.Chevrot; J ElectroanalChem 542 (2003), 33-38; (b) X.Dua, b, Z.Wang; Electrochim Acta 48 (2003), 1713-1717; (c) By Jyongsik Jang, Joonwon Bae, Eunyu Park; Adv Mater, 18 (2006), 354-358; ].Although conductive polymers is as electrode materials, had than electric capacity height, specific energy is big, advantages such as low price, but the stability of conductive polymer electrodes is also unsatisfactory regrettably, at present the cycle life that charges and discharge of the electrochemical capacitor made from it only reaches thousands of times, serious obstruction its application on producing, the cycle life that therefore improves conductive polymer electrodes is an emphasis problem of current research electrochemical capacitor.
Ionic liquid is a kind of new organic salt of broad development in recent years, and near its room temperature or room temperature (below water boiling point) is in a liquid state.Generally constitute, be also referred to as low (chamber) temperature molten salt (low/ambient/room temperaturemolten salts) by the yin, yang ion.Compare with traditional volatile organic solvent (VOC), ionic liquid has a series of outstanding advantages: 1) non-volatile or " zero " vapour pressure; 2) good electrical conductivity; 3) wide electrochemical window (＞5V); 4) Gao Re and electrochemical stability; 5) selective dissolution ability and designability.Because ionic liquid has these characteristics that conventional solvent does not possess, so they are synthetic at organic catalysis, unique effect has been brought into play in fields such as organic electrochemistry is synthetic, electrochemistry, biological chemistry, separation, provide a brand-new field [referring to (a) T.Welton to chemical research, ChemRev, 99 (1999), 2071; (b) W.Lu, A.G.Fadeev, B.Qi, E.Smela, B.R.Mattes, J.Ding, G.M.Spinks, J.Mazurkiewicz, D.Zhou, G.G.Wallace, D.R.MacFarlane, S.A.Forsyth, M.Forsyth, Science 297 (2002), and 983; (c) C.Lagrost, D.Carrie, M.Vaultier, P.Happiot, J Phys Chem A, 107 (2003), 745.].
The ion liquid reported first of distance is the history in existing 90 years so far, and its initial application promptly is as battery electrolyte.Enter after 21 century, along with the improvement of ionic liquid kind and character, it has begun to cause more and more research workers' attention.Its excellent physico-chemical property demonstrates its potential ability as capacitor electrolyte.At present its research work as electrolytic solution has been carried out nearly 10 years, obtained preferably achievement [referring to (a) Ue M, Takeda M, etc, Electrochemical and Solid-State Letters, 5 (2002), A119; (b) Ue M, Takeda M, etc, JElectrochem Soc, 150 (2003), A499; (c) Stenger-Smith JD, Webber CK, Anderson N, etc, JElectrochem Soc, 149 (2002), A973; (d) Balducci A, Bardi U, Caporali S, etc, ElectrochemCommun, 6 (2004), 566] but because electrochemical capacitor requires highly purified ionic liquid, and the present price comparison costliness of highly purified ionic liquid, thereby also limited ion liquid being extensive use of as capacitor electrolyte.
Ionic liquid is because non-volatile and non-inflammability is a kind of good green solvent; Its bigger viscosity is beneficial to the conductive film of the fine and close homogeneous of preparation; And because it contains inorganic anion in forming is convenient to the polymeric process and mixes synchronously.In view of the advantage more than it, existing document begins report and does electrolytic solution with ionic liquid, the conductive polymers that the electropolymerization preparation has special property and structure.People such as W.Lu in ionic liquid polymerization poly-polymkeric substance such as (3, the 4-ethene dioxythiophene) [referring to (a) W.Lu, A.G Fadeev, B.Qi, B.R.Mattes; Syn Meta, 135-136 (2003), 139-140; (b) P.Damlin, C.Kvarnstrom, A.Ivaska; J Electroanal Chem, 570 (2004), 113-122; (c) J.M.Pringle, M.Forsyth, D.R.MacFarlane etc; Polymer, 46 (2005), 2047-2058]; Patrick etc. have then studied usual way and have obtained the electrochemical behavior of polymkeric substance in ionic liquid [referring to (a) Patrick Soudan, Hoang Anh Ho, Daniel Belanger etc; J Electrochem Soc, 148 (2001) A775-A782; (b) Electrochem Commun, 5 (2003), 613-617].Because the conductive polymers for preparing in common water solvent or organic solvent easily has a spot of residual water-content, very big influence can be arranged like this [referring to (a) Hiroshi Harada to life-span based on the device of conductive polymers, Toshio Fuchigami, TsutomuNonaka.J.Electroanalytical.Chemistry.303 (1991), 139-150. (b) Lin Li, David C.Loveday, Dhurjati S.K.Mudigonda, John P.Ferraris.J.The Electrochemical Society.149 (2002), A1201-A1207].
Summary of the invention
The purpose of this invention is to provide a kind of new electrochemical method synthetic poly-(3, the 4-ethene dioxythiophene), it can be used as the electrode materials of ultracapacitor.
Technical scheme of the present invention is as follows:
A kind of poly-(3, the 4-ethene dioxythiophene) conductive polymers, it is characterized in that it is by 3,4-ethene dioxythiophene monomer electropolymerization, by 1-methyl-3-butyl imidazole a tetrafluoro borate as electrolytic solution and doping agent, p type doped polymer with the potentiostatic method preparation, its structure is a vesicular structure, and the surface is formed by the particle packing about 800 a large amount of nanometers to 2 micron.Its ratio electric capacity has reached 113-158F/g, and cyclical stability can reach 70,000 times.
A kind of preparation above-mentioned poly-(3, the 4-ethene dioxythiophene) method, it is as electrolytic solution and doping agent, 3 with the 1-methyl-3-butyl imidazole a tetrafluoro borate after the preparation purification, the 4-ethene dioxythiophene is a reaction monomers, and the monomer concentration scope can be at 0.05～0.5mol.L
-1Between, under the room temperature, at platinum dish working electrode, platinized platinum counter electrode; in the three-electrode system that the filamentary silver reference electrode constitutes, under the whipped state of nitrogen protection, constant potential polymerization in the potential range of 0.8～1.1V; obtain cyan film, be poly-(3, the 4-ethene dioxythiophene) of the present invention
Above-mentioned preparation method, described current potential is the current potential with respect to silver-colored reference electrode.
Of the present invention poly-(3, the 4-ethene dioxythiophene) conductive polymers is through infrared measurement, the result shows that its infrared spectrum to bibliographical information is similar substantially [referring to Kevin M ü ller, Mi-Kyoung Park, Markus Klapper, Wolfgang Knoll, Klaus M ü llen.Macromol.Chem.Phys.208 (2007), 1394-1401].By the ESEM photo, observing poly-(3, the 4-ethene dioxythiophene) of the present invention is vesicular structure, is formed by the particle packing about 800 a large amount of nanometers to 2 micron.
The model capacitor fabrication that applies to electrochemical measurement is as follows: the platinum electrode that of the present invention poly-(3, the 4-ethene dioxythiophene) that electropolymerization is obtained are modified is as working electrode, and the platinized platinum electrode is a counter electrode, and filamentary silver is a reference electrode, with 1mol.L
-1Sulphuric acid soln as electrolytic solution, with 5mv.S
-1Scanning speed on the CHI instrument, carry out scan round experiment.
Test shows, with of the present invention poly-(3, the 4-ethene dioxythiophene) as electrode materials, carry out circulation experiment, have typical capacitor specific characteristics between-0.2～0.8 volt (current potential is with respect to silver-colored reference electrode), the electrode materials electrochemical properties is stable, has reached 130F/g than electric capacity, cyclical stability has reached 70,000 times.
Description of drawings
Fig. 1 is the INFRARED SPECTRUM line chart of poly-(3, the 4-ethene dioxythiophene) of the present invention.
Fig. 2 is the ESEM shape appearance figure of poly-(3, the 4-ethene dioxythiophene) of the present invention.
Fig. 3 is poly-(3, the 4-ethene dioxythiophene) " cyclic voltammetric " figure under the scanning speed of 50mv/s of the embodiment of the invention 1 preparation.Among the figure a be in 1-methyl-3 butyl imidazole a tetrafluoro borate, prepare poly-(3, the 4-ethene dioxythiophene) cyclic voltammogram, b is the cyclic voltammogram that gathers (3, the 4-ethene dioxythiophene) for preparing in the acetonitrile electrolytic solution of the lithium perchlorate salt of 0.1mol.L-1.Its current-voltage response of PEDOT that can find to obtain in 1-methyl-3 butyl imidazole a tetrafluoro borate is near ideal capacitor.
Fig. 4 is the ratio electric capacity～cycle index life diagram of poly-(3, the 4-ethene dioxythiophene) modified electrode of embodiments of the invention 1 preparation, reduces slowly than electric capacity, and as seen its stability is fine.A is the cycle life figure that gathers (3, the 4-ethene dioxythiophene) for preparing in 1-methyl-3 butyl imidazole a tetrafluoro borate among the figure, and b is at 0.1mol.L
-1The acetonitrile electrolytic solution of lithium perchlorate salt in the cycle life figure of poly-(3,4-ethylene dioxy thiophene phenol) that prepare.
Fig. 5 is that the platinum electrode modified of poly-(3, the 4-ethene dioxythiophene) of the embodiment of the invention 1 preparation is at 12.5mA.cm
-2Constant current density under the charge-discharge graphic representation, charging curve and discharge curve be symmetry substantially, electrode for capacitors reaction reversibility is good.
Embodiment
The preparation of embodiment 1. poly-(3, the 4-ethene dioxythiophene)
The N-Methylimidazole is [referring to Graf, Fritz. in original patented method; Hupfer, Leopold.79-2940709,19791008.Eu Pat, 19810416.] the basis on change temperature of reaction synthetic preparation.With 40% oxalic dialdehyde, 290 grams (2 moles) and 40% formaldehyde, 150 gram (2.2 moles of l) stirring at normal temperature, thorough mixing dropwise adds the mixture that 25% methylamine, 248 grams (2.2 moles) and 25% ammoniacal liquor 164 restrain (2.6 moles), and temperature is controlled at 60～65 ℃.Dripped off in about 15 minutes, and under 65 ℃ of temperature of reaction, continued reaction about 5 hours.Underpressure distillation removes deammoniation and water.Remaining dark-brown liquid is collected 62～65 ℃ of (4mmHg) cuts (being product) again through the oil pump underpressure distillation, is light yellow transparent liquid slightly.195～197 ℃ cut is collected in the airbath air distillation, and product finally is a colourless transparent liquid, uses the potassium hydroxide drying for standby again.
1-methyl-3-imidazole-butyl bromide salt is the method with microwave hydrothermal, prepares in Panasonic (NN-S740WA-1200) microwave instrument.With 54.84 gram N-n-butyl bromide (～0.4 mole), 32.84 gram Methylimidazoles (～0.45 mole) are even with the ultrasonic thorough mixing of 20 ml waters.Under P2 power (be about 280 watts, promptly be equivalent to, microwave radiation 22 seconds), reacted 4 hours every 12 seconds gap.After reaction finishes, with the extraction of second diester, the unnecessary solvent of pressure reducing and steaming then.Replacement(metathesis)reaction in ethanol obtains 1-methyl-3-butyl imidazole a tetrafluoro borate with 1-methyl-3-imidazole-butyl bromide salt and Tetrafluoroboric acid silver salt.[referring to: (a) John S.Wilkes, Michael J.Zaworotko, Chem Commun., 113 (1992) 965-967; (b) Joan Fuller, Richard T.Carlin, Hugh C.De Long, Dustin Haworth, Chem Commun., 3 (1994) 299-300].The reaction after-filtration is removed insoluble Silver monobromide, and with activated carbon treatment activation decolouring, after-filtration was removed gac in 2 hours then.80 degree are the vacuum-drying product down.
Bromide anion and silver ions unnecessary in the product are removed with the method for constant potential.Counter electrode is a platinum electrode, and reference is a silver wire electrode.The electrolysis bromide anion adopts three-electrode system, and entire reaction is carried out under 85 degree.Gas with the generation of sodium hydroxide solution absorption system.Diameter is 1.0 millimeters a platinum dish working electrode, platinum counter electrode, filamentary silver reference electrode.Operating potential is+1.0 volts.The electrolytic silver ion at ambient temperature, with chromatographically pure stone mill rod as working electrode, platinum counter electrode, filamentary silver reference electrode, potentiostatic deposition under-0.35 volt current potential.
1-methyl-3-butyl imidazole a tetrafluoro borate after purifying with preparation is as electrolytic solution and doping agent, with 0.1mol.L
-13, the 4-ethene dioxythiophene adds wherein, stirs, logical nitrogen protection keeps being under the nitrogen atmosphere in the solution.At room temperature, with the platinum dish electrode of working, the platinized platinum counter electrode is in the three-electrode system of filamentary silver reference electrode, under the state of stirring, under the operating potential of 1.0V, the constant potential polymerization obtains cyan film, is poly-(3, the 4-ethene dioxythiophene) of the present invention, its infrared spectrogram is seen Fig. 1, and its ESEM shape appearance figure is seen Fig. 2.
The preparation of embodiment 2. poly-(3, the 4-ethene dioxythiophene)
Press the step preparation poly-(3, the 4-ethene dioxythiophene) of embodiment 1, but 3, the concentration of 4-ethene dioxythiophene is 0.05mol.L
-1, obtain the similar result of embodiment 1.
The preparation of embodiment 3. poly-(3, the 4-ethene dioxythiophene)
Press the step preparation poly-(3, the 4-ethene dioxythiophene) of embodiment 1, but 3, the concentration of 4-ethene dioxythiophene is 0.20mol.L
-1, obtain the similar result of embodiment 1.
The preparation of embodiment 4. poly-(3, the 4-ethene dioxythiophene)
Press the step preparation poly-(3, the 4-ethene dioxythiophene) of embodiment 1, but 3, the concentration of 4-ethene dioxythiophene is 0.50mol.L
-1, obtain the similar result of embodiment 1.
The preparation of embodiment 5. poly-(3, the 4-ethene dioxythiophene)
Press the step preparation poly-(3, the 4-ethene dioxythiophene) of embodiment 2, but operating potential becomes 0.8V, obtains similar result.
The preparation of embodiment 6. poly-(3, the 4-ethene dioxythiophene)
Press the step preparation poly-(3, the 4-ethene dioxythiophene) of embodiment 2, but operating potential becomes 1.1V, obtains similar result.
Embodiment 7. poly-(3, the 4-ethene dioxythiophene)
It is as follows than electric capacity scheme that embodiment 1 resulting mixture is applied to electrochemical measurement: will gather (3, the 4-ethene dioxythiophene) platinum electrode of Xiu Shiing is a working electrode, the platinized platinum counter electrode, the filamentary silver reference electrode, (occasion China in Shanghai produces at the CHI instrument, do cyclic voltammetry curve down together) and measure, electrolytic solution is 1mol.L
-1Sulfuric acid electrolyte.Measurement is calculated through circulation execution peace, is 130F/g than electric capacity, and cycle life is 70,000 times.
Embodiment 8. poly-(3, the 4-ethene dioxythiophene) is applied to the electrochemistry cyclic voltammetry experiment
It is as follows than electric capacity scheme that embodiment 2 resulting mixtures are applied to electrochemical measurement: will gather (3, the 4-ethene dioxythiophene) platinum electrode of Xiu Shiing is a working electrode, platinized platinum counter electrode, filamentary silver reference electrode, do the cyclic voltammetry curve measuring on the CHI instrument, electrolytic solution is 1mol.L
-1Sulfuric acid electrolyte.Measurement is calculated through circulation execution peace, is 158F/g than electric capacity.Cycle life is above 20,000 times.
Embodiment 9. poly-(3, the 4-ethene dioxythiophene) is applied to the electrochemistry cyclic voltammetry experiment
It is as follows than electric capacity scheme that embodiment 6 resulting mixtures are applied to electrochemical measurement: will gather (3, the 4-ethene dioxythiophene) platinum electrode of Xiu Shiing is a working electrode, platinized platinum counter electrode, filamentary silver reference electrode, do the cyclic voltammetry curve measuring on the CHI instrument, electrolytic solution is 1mol.L
-1Sulfuric acid electrolyte.Measurement is calculated through circulation execution peace, is 113F/g than electric capacity.
Claims (4)
1. one kind poly-(3, the 4-ethene dioxythiophene) conductive polymers, it is characterized in that: it is by 3,4-ethene dioxythiophene monomer electropolymerization, by 1-methyl-3-butyl imidazole a tetrafluoro borate as electrolytic solution and doping agent, p type doped polymer with the potentiostatic method preparation, its structure is a vesicular structure, and the surface is formed by the particle packing about 800 a large amount of nanometers to 2 micron.
2. one kind prepares claim 1 described poly-(3, the 4-ethene dioxythiophene) method is characterized in that: it is as electrolytic solution and doping agent, 3 with the 1-methyl-3-butyl imidazole a tetrafluoro borate after purifying, the 4-ethene dioxythiophene is a reaction monomers, and the monomer concentration scope is at 0.05～0.5mol.L
-1Between, under the room temperature, at platinum dish working electrode, platinized platinum counter electrode; in the three-electrode system that the filamentary silver reference electrode constitutes, under the state of the stirring of nitrogen protection, constant potential polymerization in the potential range of 0.8～1.1V; obtain cyan film, be poly-(3, the 4-ethene dioxythiophene).
3. preparation method according to claim 2 is characterized in that: described current potential is the current potential with respect to silver-colored reference electrode.
4. the application of described poly-(3, the 4-ethene dioxythiophene) conductive polymers of claim 1 in the preparation ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101243132A CN101307134A (en) | 2008-06-25 | 2008-06-25 | P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101243132A CN101307134A (en) | 2008-06-25 | 2008-06-25 | P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101307134A true CN101307134A (en) | 2008-11-19 |
Family
ID=40123833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101243132A Pending CN101307134A (en) | 2008-06-25 | 2008-06-25 | P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101307134A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149267A (en) * | 2013-02-06 | 2013-06-12 | 河南省科学院高新技术研究中心 | Electrochemical biosensor or detection of dopamine and its preparation method |
| CN104934632A (en) * | 2015-04-28 | 2015-09-23 | 常州大学 | Lithium-sulfur battery and preparation method thereof |
| CN108395556A (en) * | 2018-03-27 | 2018-08-14 | 中国科学院化学研究所 | A kind of high regularity polythiophene film and preparation method thereof with excellent thermoelectricity capability |
| CN111627712A (en) * | 2020-06-30 | 2020-09-04 | 郑州轻工业大学 | Doped dye-sensitized solar cell counter electrode material and preparation method and application thereof |
-
2008
- 2008-06-25 CN CNA2008101243132A patent/CN101307134A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103149267A (en) * | 2013-02-06 | 2013-06-12 | 河南省科学院高新技术研究中心 | Electrochemical biosensor or detection of dopamine and its preparation method |
| CN104934632A (en) * | 2015-04-28 | 2015-09-23 | 常州大学 | Lithium-sulfur battery and preparation method thereof |
| CN108395556A (en) * | 2018-03-27 | 2018-08-14 | 中国科学院化学研究所 | A kind of high regularity polythiophene film and preparation method thereof with excellent thermoelectricity capability |
| CN108395556B (en) * | 2018-03-27 | 2020-11-24 | 中国科学院化学研究所 | High-regularity polythiophene film with excellent thermoelectric performance and preparation method thereof |
| CN111627712A (en) * | 2020-06-30 | 2020-09-04 | 郑州轻工业大学 | Doped dye-sensitized solar cell counter electrode material and preparation method and application thereof |
| CN111627712B (en) * | 2020-06-30 | 2022-02-08 | 郑州轻工业大学 | Doped dye-sensitized solar cell counter electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bhat et al. | Recent trends in electrolytes for supercapacitors | |
| CN101696323B (en) | Method for preparing polyaniline/manganese dioxide composite material for super capacitor | |
| EP2634783A1 (en) | Composite electrode material, manufacturing method and application thereof | |
| CN101443857A (en) | Highly electron conductive polymer and electrochemical energy storage device with high capacity and high power using the same | |
| Liu et al. | Properties of polyaniline/ordered mesoporous carbon composites as electrodes for supercapacitors | |
| CN105719846B (en) | A kind of preparation method of cobalt sulfide/carbon composite and products thereof and application | |
| CN101307134A (en) | P-type doped poly (3,4-ethylene dioxy thiophen ), preparation thereof and use | |
| Yao et al. | Ultrafast high-energy micro-supercapacitors based on open-shell polymer-graphene composites | |
| JP2006351289A (en) | Manufacturing method of porous material and product using obtained porous material | |
| JP5109323B2 (en) | Electrode for electrochemical device, method for producing the same, and electrochemical device | |
| US9184401B2 (en) | Electrode body for solar cell, method for producing the electrode body, and solar cell provided with the electrode body | |
| EP3693983B1 (en) | Electrolytic capacitor and method for manufacturing same | |
| CN102558771A (en) | Poly 3,4-ethylenedioxy thiophene composite and preparation method thereof | |
| CN104672447B (en) | A kind of preparation method of high specific capacitance polypyrrole | |
| CN103325573A (en) | Method for preparing active conducting polymer hydrogel with oxidoreduction function | |
| JP2007250994A (en) | Conductive polymer redox type electrochemical element used as polar device | |
| JP6878896B2 (en) | Electrolytic capacitors and their manufacturing methods | |
| Yaqoob et al. | Polyaniline‐based materials for supercapacitors | |
| CN104610543A (en) | Conductive polymeric material | |
| Guo et al. | A thermostable ionic liquid electrolyte for wide-temperature window supercapacitor | |
| CN112103093A (en) | Application of quinacridone-based polymer as supercapacitor material | |
| Arya et al. | Polymer Electrolytes: Development and Supercapacitor Application | |
| Wallace et al. | Photoelectrochemical cells based on inherently conducting polymers | |
| JP2006310384A (en) | Process for producing porous electrode, porous electrode, and electrochemical device | |
| Santino et al. | Conducting Polymers for Electrochemical Capacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081119 |