CN110010368A - A kind of poly- 3,4- ethylenedioxy thiophene of sheet and the preparation method and application thereof - Google Patents
A kind of poly- 3,4- ethylenedioxy thiophene of sheet and the preparation method and application thereof Download PDFInfo
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- CN110010368A CN110010368A CN201910347312.2A CN201910347312A CN110010368A CN 110010368 A CN110010368 A CN 110010368A CN 201910347312 A CN201910347312 A CN 201910347312A CN 110010368 A CN110010368 A CN 110010368A
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- ethylene dioxythiophene
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims abstract description 33
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- ZTKQHJHANLVEBM-UHFFFAOYSA-N 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoic acid Chemical compound C1=2C=C(C)C(NCC)=CC=2OC2=CC(=NCC)C(C)=CC2=C1C1=CC=CC=C1C(O)=O ZTKQHJHANLVEBM-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 sulfonate ion Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- SXMUSCUQMMSSKP-UHFFFAOYSA-N [O].C=1C=CSC=1 Chemical compound [O].C=1C=CSC=1 SXMUSCUQMMSSKP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses poly- 3,4-ethylene dioxythiophenes of a kind of sheet and the preparation method and application thereof, belong to electrode for super capacitor technical field of material.The poly- 3,4-ethylene dioxythiophene of sheet, using ferric trichloride as oxidant, using orange II as surfactant and dopant, is prepared through chemical oxidising polymerisation using 3,4-ethylene dioxythiophene as monomer.Prepared by the present invention poly- 3,4- ethylenedioxy thiophene not only has apparent laminated structure, and there are the advantages such as specific capacitance is high, cyclical stability is excellent, preparation process is easy, preparation process is environmentally protective, mainly for the preparation of the electrode of supercapacitor, there is 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 poly- 3,4- ethylene of sheet
Dioxy thiophene and the preparation method and application thereof.
Background technique
Poly- 3,4- ethylenedioxy thiophene (PEDOT) is with conductivity is higher, potential window is wider and environmental stability is good
The advantages that good is a kind of electrode material of important supercapacitor.But the relative molecular mass of PEDOT is larger to lead to its reason
It is not high by specific capacitance, and the dissolubility of monomer in water is low, these all hinder PEDOT in electrode for super capacitor material side
The application in face.Currently, researcher by metal ion and Bronsted acid (hydrochloric acid, perchloric acid, polystyrolsulfon acid, p-methyl benzenesulfonic acid,
Camphorsulfonic acid etc.) it is added in PEDOT as dopant, to improve the specific capacitance and stable circulation performance of PEDOT.Jiang Jieqing
(Jiang Jieqing, Li Wei, Liu Dongzhi, Tian Jianhua, Guo Yafang, Zhou Xueqin;Poly- (3,4- ethylenedioxy thiophene)/camphorsulfonic acid
The synthesis of composite material and chemical property, fine chemistry industry, 2012,29 (6): being 541 ~ 541.) doping with camphorsulfonic acid
Agent, ferric trichloride are oxidant, have synthesized poly- 3,4-ethylene dioxythiophene/camphorsulfonic acid composite material by chemical oxidization method.
Studies have shown that composite material has good conductive property and chemical property, conductance when the two the mass ratio of the material is 2:1
Rate is 10.4 S/cm, and capacity remains at 140 F/g or more after 150 cycle charge-discharges.Chinese invention patent CN
108314780A under the action of surfactant, passes through chemical oxygen using Congo red and organic acid as dopant in water phase
Change polymerization reaction and prepare poly- 3,4-ethylene dioxythiophene crude product, then post-processed using sulfuric acid solution, prepares poly- 3,4- ethylene
Dioxy thiophene porous electrode material.Although prepared electrode material specific capacitance with higher and more excellent stable circulation
Property, but the preparation process of the electrode material is complicated, production cost is higher.
Summary of the invention
The present invention provides a kind of for this lower problem of specific capacitance of poly- 3,4-ethylene dioxythiophene in the prior art
Poly- 3,4- ethylenedioxy thiophene of shape and preparation method thereof.Poly- 3,4- ethylenedioxy thiophene prepared by the present invention not only has significantly
Laminated structure, and there are the advantages such as specific capacitance is high, cyclical stability is excellent, preparation process is easy, preparation process is environmentally protective,
Mainly for the preparation of the electrode of supercapacitor, there is significant economic value and social benefit.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of poly- 3,4-ethylene dioxythiophene of sheet be using 3,4-ethylene dioxythiophene as monomer, using ferric trichloride as oxidant,
Using orange II as surfactant and dopant, it is prepared through chemical oxidising polymerisation.
The preparation method of the poly- 3,4- ethylenedioxy thiophene of sheet the following steps are included:
(1) the orange II of 1 ~ 2 g is added in 50 ~ 100 mL deionized waters, magnetic stirs 10 ~ 30 min, preparation orange at room temperature
0.5 ~ 2 g 3,4-ethylene dioxythiophene is added in Xiang Shangshu solution for yellow II solution, and first magnetic stirs 30 ~ 60 min at room temperature,
20 ~ 60 min of ultrasound again, finally magnetic stirs 10 ~ 30 min again, prepares the mixed liquor of 3,4-ethylene dioxythiophene and orange II；
(2) 4 ~ 40 mL ferric trichloride hydrochloric acid solutions are added dropwise dropwise into the mixed liquor of 3,4-ethylene dioxythiophene and orange II,
At 10 ~ 20 DEG C, magnetic is stirred to react 12 ~ 36 h, after reaction, 200 ~ 400 mL methanol is added into reaction mixture, in room
The lower magnetic of temperature stirs 20 ~ 60 min, stands 24 ~ 48 h, through filtering, methanol and deionized water cross washing, 60 DEG C of vacuum drying 24
H prepares the poly- 3,4-ethylene dioxythiophene of the sheet.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Using: the poly- 3,4- ethylenedioxy thiophene of sheet mainly for the preparation of the electrode of supercapacitor.
Compared with the prior art, the present invention has the following advantages:
(1) present invention is doped PEDOT using orange II, passes through the sulfonate ion of orange II and 3,4- enedioxy thiophene
The coordination of the S atom of pheno, induction PEDOT strand align.Because orange II only has a sulfonate ion,
It is this to align more regular, it does not need to be post-processed with sulfuric acid to improve the regularity of PEDOT.Meanwhile orange II points
The hydroxyl of son has strongly hydrophilic, and PEDOT strand can be promoted to be unfolded, and forms laminated structure, increases the specific surface of PEDOT
Product, to improve the specific capacitance of PEDOT.
(2) compared with Congo red, the solubility of orange II in water is bigger, and therefore, the orange II in the present invention not only may be used
Using the dopant as PEDOT, it is also used as surfactant, promotes 3,4-ethylene dioxythiophene uniform in the reaction system
Dispersion.Meanwhile compared with Congo red, after reaction, excessive orange II is easier to remove, therefore, purifying of the invention
Journey is more convenient.
(3) poly- 3,4-ethylene dioxythiophene prepared by the present invention not only has apparent laminated structure, but also close in electric current
Degree is 0.2 A/g, 0.5 A/g, 1 A/g and when 2 A/g, and specific capacitance is 216 F/g, 203 F/g, 191 F/g and 179 F/g,
After 1000 circulations, capacity retention still reaches 94 % or more, that is, has specific capacitance height and cyclical stability excellent
The characteristics of, while preparation process is easy, preparation process is environmentally protective, mainly for the preparation of the electrode of supercapacitor, has aobvious
The economic value and social benefit of work.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the poly- 3,4- ethylenedioxy thiophene of sheet prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the poly- 3,4- ethylenedioxy thiophene of sheet prepared by embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of poly- 3,4- ethylenedioxy thiophene prepared by comparative example 1.
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
A kind of preparation method of the poly- 3,4-ethylene dioxythiophene of sheet, comprising the following steps:
(1) the orange II of 1.5 g is added in 75 mL deionized waters, magnetic stirs 20 min at room temperature, and it is molten to prepare orange II
1 g 3,4-ethylene dioxythiophene is added in Xiang Shangshu solution in liquid, and first magnetic stirs 45 min, then 40 min of ultrasound at room temperature,
Finally magnetic stirs 20 min again, prepares the mixed liquor of 3,4-ethylene dioxythiophene and orange II；
(2) 15 mL ferric trichloride hydrochloric acid solutions are added dropwise dropwise into the mixed liquor of 3,4-ethylene dioxythiophene and orange II, 15
At DEG C, magnetic is stirred to react 24 h, after reaction, 300 mL methanol is added into reaction mixture, at room temperature magnetic stirring 40
Min stands 36 h through filtering, methanol and deionized water cross washing, 60 DEG C of 24 h of vacuum drying and prepares the sheet poly- 3,
4- ethylenedioxy thiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Fig. 1 is the infrared spectrogram of the poly- 3,4- ethylenedioxy thiophene of sheet manufactured in the present embodiment.It can be seen from the figure that
1635 cm-1With 1382 cm-1The peak at place respectively corresponds the asymmetric stretching vibration absorption peak of C=C and C-C in thiphene ring, it was demonstrated that
It is successfully prepared poly- 3,4- ethylenedioxy thiophene.1085 cm-1With 514 cm-1The peak at place is the characteristic absorption of sulfonate group
Peak shows that orange II is successfully adulterated into poly- 3,4-ethylene dioxythiophene.
Fig. 2 is the scanning electron microscope (SEM) photograph of the poly- 3,4- ethylenedioxy thiophene of sheet manufactured in the present embodiment.It is shown in figure, the present invention
Apparent laminated structure is presented in the poly- 3,4- ethylenedioxy thiophene of preparation.This is because in the course of the polymerization process, the sulfonic acid of orange II
The coordination of the S atom of radical ion and 3,4-ethylene dioxythiophene, induction PEDOT strand align, and orange II points
Hydroxyl on son has strongly hydrophilic, and PEDOT strand is promoted to be unfolded, and forms sheet PEDOT.In addition the poly- 3,4- ethylene two of sheet
Gap in oxygen thiophene is caused by the removal orange II molecule of large scale.
Embodiment 2
A kind of preparation method of the poly- 3,4-ethylene dioxythiophene of sheet, comprising the following steps:
(1) the orange II of 1 g being added in 50 mL deionized waters, magnetic stirs 10 min at room temperature, orange II is prepared,
0.5 g 3,4-ethylene dioxythiophene is added into above-mentioned solution, first magnetic stirs 30 min, then 20 min of ultrasound at room temperature, most
Magnetic stirs 10 min again afterwards, prepares the mixed liquor of 3,4-ethylene dioxythiophene and orange II；
(2) 4 mL ferric trichloride hydrochloric acid solutions are added dropwise dropwise into the mixed liquor of 3,4-ethylene dioxythiophene and orange II, 10
At DEG C, magnetic is stirred to react 36 h, after reaction, 200 mL methanol is added into reaction mixture, at room temperature magnetic stirring 20
Min stands 24 h through filtering, methanol and deionized water cross washing, 60 DEG C of 24 h of vacuum drying and prepares the sheet poly- 3,
4- ethylenedioxy thiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Embodiment 3
A kind of preparation method of the poly- 3,4-ethylene dioxythiophene of sheet, comprising the following steps:
(1) the orange II of 2 g being added in 100 mL deionized waters, magnetic stirs 30 min at room temperature, orange II is prepared,
2 g 3,4-ethylene dioxythiophenes are added into above-mentioned solution, first magnetic stirs 60 min, then 60 min of ultrasound at room temperature, finally
Magnetic stirs 30 min again, prepares the mixed liquor of 3,4-ethylene dioxythiophene and orange II；
(2) 40 mL ferric trichloride hydrochloric acid solutions are added dropwise dropwise into the mixed liquor of 3,4-ethylene dioxythiophene and orange II, 20
At DEG C, magnetic is stirred to react 12 h, after reaction, 400 mL methanol is added into reaction mixture, at room temperature magnetic stirring 60
Min stands 48 h through filtering, methanol and deionized water cross washing, 60 DEG C of 24 h of vacuum drying and prepares the sheet poly- 3,
4- ethylenedioxy thiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Comparative example 1
A kind of preparation method of poly- 3,4-ethylene dioxythiophene, comprising the following steps:
(1) 1 g 3,4-ethylene dioxythiophene being added in 75 mL deionized waters, first magnetic stirs 45 min at room temperature, then
40 min of ultrasound, finally magnetic stirs 20 min again, prepares the dispersion liquid of 3,4-ethylene dioxythiophene；
(2) 15 mL ferric trichloride hydrochloric acid solutions are added dropwise in Xiang Shangshu mixed liquor dropwise, at 15 DEG C, magnetic is stirred to react 24 h,
After reaction, 300 mL methanol are added into reaction mixture, magnetic stirs 40 min at room temperature, stands 36 h, filtered,
Methanol and deionized water cross washing, 60 DEG C of 24 h of vacuum drying, prepare poly- 3,4-ethylene dioxythiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Fig. 3 is the scanning electron microscope (SEM) photograph of poly- 3,4- ethylenedioxy thiophene manufactured in the present embodiment.It is shown in figure, does not add orange
When yellow II, surface topography and the gap of coarse a large amount of blocks of solid accumulation is presented in the poly- 3,4-ethylene dioxythiophene for polymerizeing generation
It is less.
Comparative example 2
A kind of preparation method of poly- 3,4-ethylene dioxythiophene, comprising the following steps:
(1) 0.5 g 3,4-ethylene dioxythiophene being added in 50 mL deionized waters, first magnetic stirs 30 min at room temperature,
20 min of ultrasound again, finally magnetic stirs 10 min again, prepares the dispersion liquid of 3,4-ethylene dioxythiophene；
(2) 4 mL ferric trichloride hydrochloric acid solutions are added dropwise in Xiang Shangshu dispersion liquid dropwise, at 10 DEG C, magnetic is stirred to react 36 h.Instead
After answering, 200 mL methanol are added into reaction mixture, magnetic stirs 20 min at room temperature, stands 24 h.Through filtering, first
Pure and mild deionized water cross washing, 60 DEG C of 24 h of vacuum drying, prepare poly- 3,4-ethylene dioxythiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
Comparative example 3
A kind of preparation method of poly- 3,4-ethylene dioxythiophene, comprising the following steps:
(1) 2 g 3,4-ethylene dioxythiophenes being added in 100 mL deionized waters, first magnetic stirs 60 min at room temperature, then
60 min of ultrasound, finally magnetic stirs 30 min again, prepares the dispersion liquid of 3,4-ethylene dioxythiophene；
(2) 40 mL ferric trichloride hydrochloric acid solutions are added dropwise in Xiang Shangshu dispersion liquid dropwise, at 20 DEG C, magnetic is stirred to react 12 h.
After reaction, 400 mL methanol are added into reaction mixture, magnetic stirs 60 min at room temperature, stands 48 h.Filtered,
Methanol and deionized water cross washing, 60 DEG C of 24 h of vacuum drying, prepare poly- 3,4-ethylene dioxythiophene.
In the ferric trichloride hydrochloric acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/
L, solvent are deionized water.
80 % products, 15 % acetylene carbon blacks and 5 % Kynoar are uniformly mixed and are coated on stainless (steel) wire as work
Electrode, using platinum filament as to electrode, using saturated calomel electrode as reference electrode, using 1 mol/L aqueous sulfuric acid as electrolysis
Liquid is tested using the specific capacitance of product prepared by constant current charge-discharge method testing example and comparative example using cyclic voltammetry
The cyclical stability of product prepared by embodiment and comparative example, wherein voltage range is -0.2 ~ 0.8 V, charging and discharging currents density
0.2 A/g, 0.5 A/g, 1 A/g and 2 A/g respectively, sweep speed are 100 mV/s.Test result is as follows shown in table 1.
1 the performance test results of table
It can be seen that the polymerization that orange II is added to poly- 3,4-ethylene dioxythiophene from the test result of embodiment and comparative example
In reaction system, the specific capacitance and cyclical stability of poly- 3,4-ethylene dioxythiophene can be significantly improved.
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 (5)
1. a kind of preparation method of the poly- 3,4-ethylene dioxythiophene of sheet, it is characterised in that: poly- 3, the 4- enedioxy of sheet
Thiophene is using 3,4-ethylene dioxythiophene as monomer, using ferric trichloride as oxidant, using orange II as surfactant and doping
Agent is prepared through chemical oxidising polymerisation.
2. the preparation method of the poly- 3,4-ethylene dioxythiophene of sheet according to claim 1, it is characterised in that: including following
Step:
(1) the orange II of 1 ~ 2 g is added in 50 ~ 100 mL deionized waters, magnetic stirs 10 ~ 30 min, preparation orange at room temperature
0.5 ~ 2 g 3,4-ethylene dioxythiophene is added in Xiang Shangshu solution for yellow II solution, and first magnetic stirs 30 ~ 60 min at room temperature,
20 ~ 60 min of ultrasound again, finally magnetic stirs 10 ~ 30 min again, prepares the mixed liquor of 3,4-ethylene dioxythiophene and orange II；
(2) 4 ~ 40 mL ferric trichloride hydrochloric acid solutions are added dropwise dropwise into the mixed liquor of 3,4-ethylene dioxythiophene and orange II,
At 10 ~ 20 DEG C, magnetic is stirred to react 12 ~ 36 h, after reaction, 200 ~ 400 mL methanol is added into reaction mixture, in room
The lower magnetic of temperature stirs 20 ~ 60 min, stands 24 ~ 48 h, through filtering, methanol and deionized water cross washing, 60 DEG C of vacuum drying 24
H prepares the poly- 3,4-ethylene dioxythiophene of the sheet.
3. the preparation method of the poly- 3,4-ethylene dioxythiophene of sheet according to claim 2, it is characterised in that: described three
In iron chloride salt acid solution, the concentration of ferric trichloride is 2 mol/L, and the concentration of hydrochloric acid is 0.02 mol/L, and solvent is deionization
Water.
4. the poly- 3,4- ethylenedioxy thiophene of sheet made from preparation method a method according to any one of claims 1-3.
5. a kind of poly- 3,4- ethylenedioxy thiophene of sheet as claimed in claim 4 answering in the electrode of preparation supercapacitor
With.
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| CN112185711A (en) * | 2020-10-13 | 2021-01-05 | 福州大学 | Preparation method of poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material |
| CN112201486A (en) * | 2020-10-13 | 2021-01-08 | 福州大学 | Preparation method of poly (3, 4-ethylenedioxythiophene)/graphite felt flexible electrode material |
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