CN108314780B - A kind of preparation method of highly conductive poly- 3,4- ethylenedioxy thiophene porous electrode material - Google Patents
A kind of preparation method of highly conductive poly- 3,4- ethylenedioxy thiophene porous electrode material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of highly conductive poly- 3,4-ethylene dioxythiophene porous electrode material, belong to electrode for super capacitor technical field of material.It is to be dissolved in water Congo red and surfactant, Congo red and surfactant mixed solution is made, then to mixed solution and dripping organic acid to adjust its pH value, 3,4-ethylene dioxythiophene and oxidant are successively added drop-wise in gained mixed solution again, obtain poly- 3 through chemical oxidising polymerisation, 4- ethylenedioxy thiophene crude product, it is filtered, washed, dries after being impregnated again using sulfuric acid solution, obtain the poly- 3,4-ethylene dioxythiophene porous electrode material.Electrode material prepared by the present invention not only has apparent porous structure, and its conductivity is big, specific capacitance is high, with excellent cyclical stability, while the raw material for preparing the electrode material are easy to get, are cheap, preparation process is environmentally protective, yield is high, have significant economic value and social benefit.
Description
Technical field
The invention belongs to electrode for super capacitor technical field of material, and in particular to a kind of highly conductive poly- 3,4- second
Support the preparation method of dioxy thiophene porous electrode material.
Background technique
Poly- 3,4- ethylenedioxy thiophene is due to special, regular orderly planarization molecular structure and stable conduction
State is with a wide range of applications in terms of the electrode material of supercapacitor.But high relative molecular mass makes its reason
It can only achieve 210 F/g by specific capacity, while the conductivity of undoped poly- 3,4-ethylene dioxythiophene is relatively low, these are all limited
Its application in terms of electrode material is made.
Cui Chenchen (Cui Chenchen, Wang Ming " preparation of conducting polymer PEDOT and electric conductivity " HeFei University of Technology
Journal (natural science edition), 2012,35 (11): 1541-1545) in order to improve the conductivity of poly- 3,4-ethylene dioxythiophene,
Using ammonium persulfate as oxidant, a variety of Bronsted acids are dopant, have synthesized form of spherical particles poly- 3 using chemical oxidative polymerization,
4- ethylenedioxy thiophene, the study found that its conductivity can be significantly improved after the doping of hydrochloric acid, glacial acetic acid and camphorsulfonic acid,
Conductivity after middle camphorsulfonic acid doping can achieve 0.293 S/cm, than the conductivity undoped with poly- 3,4-ethylene dioxythiophene
Improve 1 order of magnitude.Using water as solvent in patent of invention CN 102558771A, organic acid is made poly- 3 as dopant,
4- ethylenedioxy thiophene electrode material, the specific capacitance of the electrode material can reach 150 F/g, but its that there are polymerization yield rates is low, gather
The problems such as 3,4- ethylenedioxy thiophene pattern is more difficult to control.
The present invention is using Congo red and organic acid as dopant, under the action of surfactant, the passing through in water phase
It learns oxidative polymerization method and prepares the poly- 3,4-ethylene dioxythiophene porous electrode material of high yield, and after being carried out with sulfuric acid solution
Processing, to further increase the conductivity and specific capacitance of the electrode material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation sides of highly conductive poly- 3,4- ethylenedioxy thiophene porous electrode material
Method, the electrode obtained material not only have apparent porous structure, and its conductivity is big, specific capacitance is high, steady with excellent circulation
It is qualitative, while the raw material for preparing the electrode material are easy to get, are cheap, preparation process is environmentally protective, yield is high, have significant
Economic value and social benefit.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of highly conductive poly- 3,4-ethylene dioxythiophene porous electrode material, is with Congo red and organic
Acid is used as dopant, under the action of surfactant, prepares poly- 3,4- ethylene by chemical oxidising polymerisation reaction in water phase
Dioxy thiophene crude product, then post-processed using sulfuric acid solution, obtain the poly- 3,4-ethylene dioxythiophene porous electrode material；
Specific preparation process is as follows for it:
(1) 0.1 ~ 0.5g is Congo red and 0.5 ~ 3mmol surfactant is added in 100mL deionized water, at 50 DEG C
20 ~ 40min is stirred, Congo red and surfactant mixed solution is made, then to the mixed solution and dripping organic acid, until
The pH value of mixed solution is 1 ~ 3；
(2) by the oxidant ammonium persulfate aqueous solution of 1 mol/L of 0.2 ~ 4g 3,4- ethylenedioxy thiophene and 1 ~ 80mL according to
In the secondary mixed solution for being added drop-wise to step (1) preparation, be stirred to react 12 at 40 ~ 70 DEG C ~ for 24 hours after, methanol is added and is settled,
Gained sedimentation products successively use dehydrated alcohol and deionized water cross washing to filtrate to clarify, and obtain blackish green poly- 3,4- ethylene two
Oxygen thiophene crude product；
(3) poly- 3,4-ethylene dioxythiophene crude product made from step (2) is immersed in 1mol/L sulfuric acid solution, ultrasound point
24 ~ 72h is stood after dissipating 1 ~ 4h, filtering, product is washed to filtrate with methanol and is in neutrality, then is dried in vacuo for 24 hours at 60 DEG C, is obtained
Poly- 3,4- ethylenedioxy thiophene porous electrode material.
The surfactant is dodecyl sodium sulfate, lauryl sodium sulfate, neopelex or amber
Any one in acid esters sodium sulfonate.
The organic acid is any one in p-methyl benzenesulfonic acid, camphorsulfonic acid or lignin sulfonic acid.
Two Congo red azochlorosulfonate acid anions connect with positively charged poly- 3,4- ethylenedioxy thiophene molecule segment respectively
It connects, increases the intramolecular conductive network of poly- 3,4-ethylene dioxythiophene, improve the transport efficiency of electronics, so as to improve electricity
The conductivity and specific capacitance of pole material, while Congo red can also to stablize positively charged poly- 3,4-ethylene dioxythiophene oligomeric
Object promotes oligomer further occurrence chemical oxidation reaction and effectively improves yield, and guarantees poly- 3,4-ethylene dioxythiophene tool
There is long conjugated chain；And the organic acid doped state of oxidation that can be effectively improved poly- 3,4-ethylene dioxythiophene, improve its electricity
Conductance.Surfactant can effectively facilitate the dissolution of 3,4-ethylene dioxythiophene monomer in water, further increase poly- 3,4-
The yield of ethylenedioxy thiophene, while under the action of surfactant, the strand of poly- 3,4-ethylene dioxythiophene can be sent out
The arrangement of raw orientation, to obtain the poly- 3,4-ethylene dioxythiophene with porous structure, which increases electrode material
The contact area of material and electrolyte, so that the specific capacitance of poly- 3,4-ethylene dioxythiophene can be improved.Using sulfuric acid solution to poly- 3,
4- ethylenedioxy thiophene is post-processed, and can be further improved the crystallinity and doping level of poly- 3,4-ethylene dioxythiophene,
To further increase the conductivity and specific capacitance of porous electrode material.
Remarkable advantage of the invention is:
(1) raw material of the present invention are easy to get, are cheap, use water as polymerization solvent, and preparation process is environmentally protective,
And the dissolubility of 3,4-ethylene dioxythiophene monomer in water can be improved by the way that surfactant and organic acid etc. is added, solve
The 3,4-ethylene dioxythiophene universal lower disadvantage of polymerization yield rate in water, makes the yield of electrode material up to 83 %.
(2) poly- 3,4-ethylene dioxythiophene prepared by the present invention not only has apparent porous structure, but also its conductivity
Up to 127 S/cm, 5 orders of magnitude are improved than undoped poly- 3,4-ethylene dioxythiophene；It is 1 g/ in charging and discharging currents density
When A, specific capacitance improves 228 % up to 197 F/g, than undoped poly- 3,4-ethylene dioxythiophene；It is recycled by 2000 times
Afterwards, capacity retention still reaches 87 %, that is, has the cyclical stability that conductivity is big, specific capacitance is high and excellent.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared of poly- 3,4- ethylenedioxy thiophene porous electrode material prepared by embodiment 1
Spectrum；
Fig. 2 is the scanning electron microscope (SEM) photograph of poly- 3,4- ethylenedioxy thiophene porous electrode material prepared by embodiment 1；
Fig. 3 is the poly- 3,4- enedioxy thiophene that the preparation of Congo red and surfactant is not added under 1 the same terms of embodiment
The scanning electron microscope (SEM) photograph of pheno electrode material.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
(1) by 0.25g is Congo red and 1.25mmol Disodium sulfosuccinate is added in 100mL deionized water, at 50 DEG C
30min is stirred, Congo red and Disodium sulfosuccinate mixed solution is made, then to the mixed solution and dripping camphor sulphur
Acid, until the pH value of mixed solution is 2；
(2) 1.25g 3,4- ethylenedioxy thiophene and 1 mol/L ammonium persulfate aqueous solution of 13mL are successively added drop-wise to step
(1) prepare mixed solution in, after being stirred to react 18h at 55 DEG C, be added methanol settled, filtered sedimentation products according to
It is secondary to be clarified with dehydrated alcohol and deionized water cross washing to filtrate, obtain blackish green poly- 3,4-ethylene dioxythiophene crude product；
(3) poly- 3,4-ethylene dioxythiophene crude product made from step (2) is immersed in 1 mol/L sulfuric acid solution, ultrasound
48h is stood after dispersion 2.5h, is filtered, product is washed to filtrate with methanol and is in neutrality, then is dried in vacuo for 24 hours at 60 DEG C, is obtained
Poly- 3,4- ethylenedioxy thiophene porous electrode material.
Fig. 1 is the Fourier transform infrared of poly- 3,4- ethylenedioxy thiophene porous electrode material manufactured in the present embodiment
Spectrum.It will be seen from figure 1 that 1480 cm-1With 1310 cm-1The peak at place respectively corresponds the asymmetry of C=C and C-C in thiphene ring
Stretching vibration absworption peak, 1514 cm-1With 979 cm-1The peak at place is the C-O-C stretching vibration absworption peak of ethylenedioxy, it was demonstrated that at
Function is prepared for poly- 3,4- ethylenedioxy thiophene.1174 cm-1、1186 cm-1With 676 cm-1The peak at place is the spy of sulfonate group
Absorption peak is levied, shows that Congo red successfully doping enters poly- 3,4-ethylene dioxythiophene.
Fig. 2 is the scanning electron microscope (SEM) photograph of poly- 3,4- ethylenedioxy thiophene porous electrode material manufactured in the present embodiment.Fig. 3 is this
Sweeping for the poly- 3,4- ethylenedioxy thiophene electrode material of Congo red and surfactant preparation is not added under embodiment the same terms
Retouch electron microscope.By Fig. 2,3 comparison as it can be seen that poly- 3,4-ethylene dioxythiophene porous electrode material prepared by the present invention present it is fluffy
Nutty structure, and there are apparent holes between particle；When without adding Congo red and surfactant, it polymerize generation
The surface topography without duct densification is presented in electrode material.This is because in the course of the polymerization process, poly- 3,4-ethylene dioxythiophene is easy
Reunite, and it is Congo red have stabilization to poly- 3,4-ethylene dioxythiophene oligomer, can effectively inhibit poly- 3,4- ethylene two
The reunion of oxygen thiophene, surfactant can effectively control poly- 3,4-ethylene dioxythiophene strand and align, to be formed
Poly- 3,4- ethylenedioxy thiophene porous electrode material with regular pattern.
The yield of electrode material manufactured in the present embodiment reaches 83 %；Conductivity reaches 127 S/cm, more poly- than undoped
The conductivity of 3,4- ethylenedioxy thiophene improves 5 orders of magnitude；When charging and discharging currents density is 1 g/A, specific capacitance reaches
197 F/g, the specific capacitance than undoped poly- 3,4-ethylene dioxythiophene improve 228 %；After 2000 circulations, electricity
Hold conservation rate and still reaches 87 %.In contrast, it is added without obtained blackish green poly- 3 in the case of Congo red and surfactant,
4- ethylenedioxy thiophene electrode material, yield are only 10.6 %, and conductivity is 1.05 S/cm, are 1 in charging and discharging currents density
When g/A, specific capacitance is 102 F/g.
Embodiment 2
(1) it by 0.1g is Congo red and 0.5mmol dodecyl sodium sulfate is added in 100mL deionized water, is stirred at 50 DEG C
20min is mixed, Congo red and dodecyl sodium sulfate mixed solution is made, then to the mixed solution and dripping to methylbenzene sulphur
Acid, until the pH value of mixed solution is 3；
(2) 0.2g 3,4- ethylenedioxy thiophene and 1 mol/L ammonium persulfate aqueous solution of 1mL are successively added drop-wise to step
(1) prepare mixed solution in, after being stirred to react 12h at 40 DEG C, be added methanol settled, filtered sedimentation products according to
It is secondary to be clarified with dehydrated alcohol and deionized water cross washing to filtrate, obtain blackish green poly- 3,4-ethylene dioxythiophene crude product；
(3) poly- 3,4-ethylene dioxythiophene crude product made from step (2) is immersed in 1 mol/L sulfuric acid solution, ultrasound
It is stood for 24 hours after dispersion 1h, filtering, product is washed to filtrate with methanol and is in neutrality, then is dried in vacuo for 24 hours at 60 DEG C, is gathered
3,4- ethylenedioxy thiophene porous electrode material.
The yield of electrode material manufactured in the present embodiment reaches 74 %；Conductivity reaches 21 S/cm, than undoped poly- 3,
The conductivity of 4- ethylenedioxy thiophene improves 4 orders of magnitude；When charging and discharging currents density is 1 g/A, specific capacitance reaches 128
F/g, the specific capacitance than undoped poly- 3,4-ethylene dioxythiophene improve 113 %；After 2000 circulations, capacitor is protected
Holdup still reaches 84 %.In contrast, it is added without blackish green poly- 3,4- second obtained in the case of Congo red and surfactant
Dioxy thiophene electrode material is supportted, it is 1 g/A in charging and discharging currents density that yield, which is only 12.0 %, and conductivity is 0.89 S/cm
When, specific capacitance is 90 F/g.
Embodiment 3
(1) it by 0.5g is Congo red and 3mmol neopelex is added in 100mL deionized water, is stirred at 50 DEG C
40min is mixed, Congo red and neopelex mixed solution is made, then to the mixed solution and dripping sulfomethylated lignin
Acid, until the pH value of mixed solution is 1；
(2) 4g 3,4- ethylenedioxy thiophene and 1 mol/L ammonium persulfate aqueous solution of 80mL are successively added drop-wise to step (1)
In the mixed solution of preparation, after being stirred to react for 24 hours at 70 DEG C, methanol is added and is settled, filtered sedimentation products are successively
It is clarified with dehydrated alcohol and deionized water cross washing to filtrate, obtains blackish green poly- 3,4-ethylene dioxythiophene crude product；
(3) poly- 3,4-ethylene dioxythiophene crude product made from step (2) is immersed in 1 mol/L sulfuric acid solution, ultrasound
72h is stood after dispersion 4h, is filtered, product is washed to filtrate with methanol and is in neutrality, then is dried in vacuo for 24 hours at 60 DEG C, is gathered
3,4- ethylenedioxy thiophene porous electrode material.
The yield of electrode material manufactured in the present embodiment reaches 78 %；Conductivity reaches 67 S/cm, than undoped poly- 3,
The conductivity of 4- ethylenedioxy thiophene improves 4 orders of magnitude；When charging and discharging currents density is 1 g/A, specific capacitance reaches 158
F/g, the specific capacitance than undoped poly- 3,4-ethylene dioxythiophene improve 163 %；After 2000 circulations, capacitor is protected
Holdup still reaches 85 %.In contrast, it is added without blackish green poly- 3,4- second obtained in the case of Congo red and surfactant
Dioxy thiophene electrode material is supportted, it is 1 g/A in charging and discharging currents density that yield, which is only 12.1 %, and conductivity is 0.95 S/cm
When, specific capacitance is 96 F/g.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of preparation method of highly conductive poly- 3,4-ethylene dioxythiophene porous electrode material, it is characterised in that: with Congo red
With organic acid as dopant, under the action of surfactant, poly- 3 are prepared by chemical oxidising polymerisation reaction in water phase,
4- ethylenedioxy thiophene crude product, then post-processed using sulfuric acid solution, obtain the porous electricity of poly- 3,4-ethylene dioxythiophene
Pole material；
The specific steps of which are as follows:
(1) 0.1 ~ 0.5g is Congo red and 0.5 ~ 3mmol surfactant is added in 100mL deionized water, it is stirred at 50 DEG C
Congo red and surfactant mixed solution is made in 20 ~ 40min, then to the mixed solution and dripping organic acid, until mixing
The pH value of solution is 1 ~ 3；
(2) the oxidant ammonium persulfate aqueous solution of 1 mol/L of 0.2 ~ 4g 3,4- ethylenedioxy thiophene and 1 ~ 80mL is successively dripped
It is added in the mixed solution of step (1) preparation, it is stirred to react 12 at 40 ~ 70 DEG C ~ for 24 hours, obtain blackish green poly- 3,4- ethylene two
Oxygen thiophene crude product；
(3) poly- 3,4-ethylene dioxythiophene crude product made from step (2) is immersed in 1mol/L sulfuric acid solution, ultrasonic disperse 1 ~
24 ~ 72h is stood after 4h, filtering, product is washed to filtrate with methanol and is in neutrality, then is dried in vacuo for 24 hours at 60 DEG C, poly- 3 are obtained,
4- ethylenedioxy thiophene porous electrode material.
2. the preparation method of highly conductive poly- 3,4-ethylene dioxythiophene porous electrode material according to claim 1, special
Sign is: the surfactant is dodecyl sodium sulfate, lauryl sodium sulfate, neopelex or succinic acid
Any one in ester sodium sulfonate.
3. the preparation method of highly conductive poly- 3,4-ethylene dioxythiophene porous electrode material according to claim 1, special
Sign is: the organic acid is any one in p-methyl benzenesulfonic acid, camphorsulfonic acid or lignin sulfonic acid.
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