CN109320717A - The preparation method of a kind of nanometer of linear electrically conductive polyaniline gel and its application in supercapacitor - Google Patents
The preparation method of a kind of nanometer of linear electrically conductive polyaniline gel and its application in supercapacitor Download PDFInfo
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- CN109320717A CN109320717A CN201710641488.XA CN201710641488A CN109320717A CN 109320717 A CN109320717 A CN 109320717A CN 201710641488 A CN201710641488 A CN 201710641488A CN 109320717 A CN109320717 A CN 109320717A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 26
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 46
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000005457 ice water Substances 0.000 claims description 22
- 239000003990 capacitor Substances 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000009954 braiding Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 235000012149 noodles Nutrition 0.000 claims description 2
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000002468 redox effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses the preparation method of a kind of nanometer of linear electrically conductive polyaniline gel and its applications in terms of supercapacitor, nanometer threadiness electrically conductive polyaniline gel is synthesized using tetraphenylporphyrin tetrasulfonic acid as crosslinking agent, a plurality of polyaniline molecule chain is crosslinked using polybasic sulfoacid and protonic acid doping synthesizes nanometer threadiness polyaniline gel, it is free of non-conductive polymer, and there is big specific surface area, excellent electric conductivity and good chemical property；Used preparation method is quick and easy, non-environmental-pollution, is suitble to industrialized production；Prepared nanometer threadiness electrically conductive polyaniline gel electrode can be used for supercapacitor, at room temperature, has apparent redox property, excellent high rate performance and cycle life, is able to satisfy requirement of the supercapacitor to high performance electrode material.
Description
Technical field
The invention belongs to conducting polymer fields, more particularly to the preparation side of a kind of nanometer of linear electrically conductive polyaniline gel
Method and its application in terms of supercapacitor.
Background technique
Conductive polymer gel is particular polymer material that is a kind of while having both gel and organic conductor excellent properties.It receives
The conductive polymer gel of rice structure has a three-dimensional organic conductive network, internal micro-nano hole and intrinsic molten of molecule interchain
Swollen characteristic, can for electronics and ion transmission express passway be provided, have faster electrochemical reaction speed, and can maintain compared with
Strong structural stability.Therefore, in recent years conductive polymer gel be considered as a kind of great potential supercapacitor or lithium
Ion battery electrode materials.The conductive agent and binder in conventional lithium ion battery are substituted for example, by using conductive polymer gel,
Or when being directly used as electrode of super capacitor, thus electrolyte can be directly entered its internal micro-nano duct, be more advantageous to
Active material comes into full contact with.Conductive polymer gel has shorter lithium ion transport road relative to traditional two-dimensional film
Diameter can significantly improve chemical property of the electrode material in high power charging-discharging.
However, conductive polymer gel monomer, is usually added to non-conductive by a large amount of research work both at home and abroad at present
It polymerize in gel-in-matrix, or gel component is blended with conducting polymer directly and is made, causes in conductive polymer gel often
Containing a large amount of non-conductive ingredients, and conducting polymer may be separated with matrix when gel swelling, so that conductivity and stability are poor,
It is difficult to meet specifically used requirement, limits its application on high-performance equipment.It therefore, is realization conductive polymer gel energy
The novel processing step of conductive polymer gel is studied in extensive use in fields such as energy storage devices, by microstructure design with
Regulation synthesizing new conductive polymer gel material has a very important significance.
Summary of the invention
For the deficiencies in the prior art, the purpose of the present invention is to provide a kind of nanometer of linear electrically conductive polyaniline is solidifying
The preparation method of glue and its application in terms of supercapacitor are synthesized using tetraphenylporphyrin tetrasulfonic acid (TPPS) as crosslinking agent
The linear electrically conductive polyaniline gel of nanometer, one side multi-sulfonic group are cross-linked to form three-dimensional gel structure with polyaniline molecule chain, keep away
The introducing of non-conductive ingredient is exempted from, the electric conductivity of polyaniline gel is on the other hand improved by protonic acid doping, to be made
More excellent performance of nanometer threadiness electrically conductive polyaniline gel.Meanwhile the nanometer being crosslinked with tetraphenylporphyrin tetrasulfonic acid (TPPS)
Linear polyaniline gel is electrode material, is applied in supercapacitor, capacitor and performance as electrode of super capacitor are ground
Study carefully, nanometer threadiness polyaniline gel is applied directly on collector, the amount of inert matter in electrode is reduced.
The present invention is achieved by the following technical solutions:
A kind of nanometer of linear electrically conductive polyaniline gel, makees crosslinking agent and dopant with tetraphenylporphyrin tetrasulfonic acid (TPPS),
A plurality of polyaniline molecule chain is crosslinked using polybasic sulfoacid and protonic acid doping synthesizes nanometer threadiness polyaniline gel, polyaniline nano
The tridimensional network that the braiding that is cross-linked with each other, interts and tangles between line is constituted, polyaniline nano-line surface present uniformly intensive
Burr shape, there are tiny gaps at part polyaniline nano-line center.
Moreover, the polyaniline nano-line is of uniform size, diameter 120-180nm.
A kind of preparation method of nanometer of linear electrically conductive polyaniline gel, comprising the following steps:
(1) tetraphenylporphyrin tetrasulfonic acid and aniline are dispersed in distilled water, ice-water bath is carried out after ultrasonic agitation；Its
The dosage of middle tetraphenylporphyrin tetrasulfonic acid is 0.1-5 molar part, and every part is 1mmol, and the dosage of aniline is 2-6 molar part, every part
For 1mmol；
(2) ammonium persulfate is dispersed in distilled water, then carries out ice-water bath；The wherein quality and step of ammonium persulfate
Suddenly the aniline equimolar ratio in (1)；
(3) solution that step (2) obtains is added in the solution that step (1) obtains, standing after stirring makes aniline polymerization
Completely, it washs and is freeze-dried to obtain nanometer threadiness electrically conductive polyaniline gel.
Moreover, the volume of distilled water is 1-4 parts by volume in above-mentioned steps (1), every parts by volume is 1mL, and the time is stirred by ultrasonic
For 30min, the temperature of ice-water bath is 0-4 DEG C.
Moreover, the volume of distilled water is 0.5~3 parts by volume in above-mentioned steps (2), every parts by volume is 1mL, the temperature of ice-water bath
Degree is 0-4 DEG C.
Moreover, mixing time is 1~60s in above-mentioned steps (3), time of repose is 12~48h, sublimation drying 12
~48h.
Moreover, according to the nanometer threadiness electrically conductive polyaniline gel of above-mentioned preparation method preparation with tetraphenylporphyrin tetrasulfonic acid
(TPPS) make crosslinking agent and dopant, be crosslinked a plurality of polyaniline molecule chain using polybasic sulfoacid and protonic acid doping synthesizes nano wire
Shape polyaniline gel, the tridimensional network that the braiding that is cross-linked with each other, interts and tangles between polyaniline nano-line is constituted, polyaniline
Uniformly intensive burr shape is presented in nanowire surface, and there are tiny gaps at part polyaniline nano-line center.
Moreover, the polyaniline nano-line is of uniform size, diameter 120-180nm.
A kind of preparation method of nanometer of linear electrically conductive polyaniline gel electrode, comprising the following steps:
(1) tetraphenylporphyrin tetrasulfonic acid and aniline are dispersed in distilled water, ice-water bath is carried out after ultrasonic agitation；Its
The dosage of middle tetraphenylporphyrin tetrasulfonic acid is 0.1-5 molar part, and every part is 1mmol, and the dosage of aniline is 2-6 molar part, every part
For 1mmol；
(2) ammonium persulfate is dispersed in distilled water, then carries out ice-water bath；The wherein quality and step of ammonium persulfate
Suddenly the aniline equimolar ratio in (1)；
(3) solution that step (2) obtains is added in the solution that step (1) obtains, standing after stirring makes aniline polymerization
Completely, it washs and is freeze-dried to obtain nanometer threadiness electrically conductive polyaniline gel；
(4) carbon paper is dried after distilled water and ethyl alcohol distinguish repeated flushing, the nanometer that then step (3) is prepared
Line-shaped conductive polyaniline gel is uniformly spun on above-mentioned carbon paper, and nanometer threadiness electrically conductive polyaniline gel is made by being dried in vacuo
Electrode.
Moreover, the volume of distilled water is 1-4 parts by volume in above-mentioned steps (1), every parts by volume is 1mL, and the time is stirred by ultrasonic
For 30min, the temperature of ice-water bath is 0-4 DEG C.
Moreover, the volume of distilled water is 0.5~3 parts by volume in above-mentioned steps (2), every parts by volume is 1mL, the temperature of ice-water bath
Degree is 0-4 DEG C.
Moreover, mixing time is 1~60s in above-mentioned steps (3), time of repose is 12~48h, sublimation drying 12
~48h.
Moreover, the nanometer threadiness electrically conductive polyaniline gel being spun on described in above-mentioned steps (4) on carbon paper with a thickness of 20-
50μm。
Application of a kind of nanometer of linear electrically conductive polyaniline gel electrode in supercapacitor, at room temperature, after freeze-drying
Polyaniline gel by four probe resistance rate testers measure its conductivity be 0.2-0.35S/cm, existed using three-electrode system
The H of 1.0M2SO4Electro-chemical test is carried out in electrolyte, the circulation volt at 5~200mV/s scanning speed, voltage -0.2-0.8V
Nanometer threadiness electrically conductive polyaniline gel electrode has apparent redox property to peace as the result is shown；It is tested using time voltage method
Capacitor of the polyaniline gel electrode under different current densities, when current density is 0.5A/g, capacitor is 300-350F/g,
When current density is 10A/g, capacitor is still up to 180-190F/g.
Application of a kind of nanometer of linear electrically conductive polyaniline gel in supercapacitor, nanometer threadiness electrically conductive polyaniline is coagulated
Glue is uniformly spun on carbon paper, and nanometer threadiness electrically conductive polyaniline gel electrode, this nanometer of line-shaped conductive is made by being dried in vacuo
Polyaniline gel application of electrode tests polyaniline gel electrode in different electric currents in supercapacitor, using time voltage method
Capacitor under density, when current density is 0.5A/g, capacitor is 300-350F/g, and when current density is 10A/g, capacitor is still
So up to 180-190F/g.
The beneficial effects of the present invention are:
(1) present invention makees crosslinking agent and dopant with tetraphenylporphyrin tetrasulfonic acid (TPPS), is crosslinked using polybasic sulfoacid more
Polyaniline molecule chain and protonic acid doping synthesize nanometer threadiness polyaniline gel, are free of non-conductive polymer, and have big
Specific surface area, excellent electric conductivity and good chemical property；
(2) preparation method of the present invention is quick and easy, non-environmental-pollution, is suitble to industrialized production；
(3) the nanometer threadiness electrically conductive polyaniline gel electrode prepared by the present invention can be used for supercapacitor, in room temperature
Under, there is apparent redox property, excellent high rate performance and cycle life, be able to satisfy supercapacitor to high-performance electric
The requirement of pole material.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of nanometer threadiness electrically conductive polyaniline gel prepared by embodiment 1；
Fig. 2 be embodiment 2 prepare nanometer threadiness electrically conductive polyaniline gel transmission electron microscope photo；
Fig. 3 is the stereoscan photograph of nanometer threadiness electrically conductive polyaniline gel prepared by embodiment 3；
Fig. 4 is the cyclic voltammetry curve of nanometer threadiness electrically conductive polyaniline gel electrode prepared by embodiment 4；
Fig. 5 is time-measuring electric potential (E-t) curve of nanometer threadiness electrically conductive polyaniline gel electrode prepared by embodiment 4；
Fig. 6 is the cycle life curve of nanometer threadiness electrically conductive polyaniline gel electrode prepared by embodiment 4；
Fig. 7 is the impedance spectra of nanometer threadiness electrically conductive polyaniline gel electrode prepared by embodiment 4.
Specific embodiment
Below with reference to Fig. 1 to a kind of nanometer of the present invention shown in Fig. 7 linear electrically conductive polyaniline gel preparation method and its
Present invention is further described in detail for the specific embodiment of application in terms of supercapacitor.Under it should be understood that
State embodiment be it is illustrative, be not restrictive, cannot be limited the scope of protection of the present invention with following embodiments.
Embodiment 1
The aniline of 2mmol and 1mmol tetraphenylporphyrin tetrasulfonic acid (TPPS) are dissolved in 1mL distilled water, are stirred by ultrasonic
30min makes it sufficiently dissolve mixing, then places it in 0 DEG C of ice-water bath；The ammonium persulfate of 1mmol is dissolved in 0.5mL distilled water
In, it is subsequently placed in 0 DEG C of ice-water bath；It will finally rapidly join dissolved with the solution of ammonium persulfate dissolved with aniline and tetraphenylporphyrin four
In the solution of sulfonic acid (TPPS), reaction 12h is stood after stirring 10s, polyaniline gel is formed, is then washed with distilled water 2-3 times；
It is freeze-dried the polyaniline gel of above-mentioned preparation to obtain product.Electrically conductive polyaniline gel obtained is passed through into scanning electron microscopy
Mirror (SEM) analysis, as shown in Figure 1, tetraphenylporphyrin tetrasulfonic acid (TPPS) crosslinking polyaniline gel is interspersed by being cross-linked with each other
Polyaniline nano-line composition.The braiding that is cross-linked with each other, interts and tangles between polyaniline nano-line constitutes tridimensional network.It is poly-
Aniline nano line it is of uniform size, the node of nano wire bifurcated is apart from each other, be 500nm to 1.5 μm.By the polyaniline after freeze-drying
It is 0.28S/cm that gel, which measures its conductivity by four probe resistance rate testers, and the polyaniline much higher than conventional method preparation is solidifying
Glue.
Embodiment 2
The aniline of 4mmol and 3mmol tetraphenylporphyrin tetrasulfonic acid (TPPS) are dissolved in 2mL distilled water, are stirred by ultrasonic
30min makes it sufficiently dissolve mixing, then places it in 2 DEG C of ice-water baths；The ammonium persulfate of 2.5mmol is dissolved in 1mL distilled water
In, it is subsequently placed in 2 DEG C of ice-water baths；It will finally rapidly join dissolved with the solution of ammonium persulfate dissolved with aniline and tetraphenylporphyrin four
In the solution of sulfonic acid (TPPS), reaction is stood for 24 hours after ultrasonic 15s, is formed polyaniline gel, is then washed with distilled water 2-3 times；
It is freeze-dried the polyaniline gel of above-mentioned preparation to obtain product.By electrically conductive polyaniline gel obtained by tem analysis, such as scheme
Shown in 2, the mutually interspersed entanglement of polyaniline nano-line skeleton of gel is constituted, polyaniline gel has apparent three-dimensional netted knot
Structure.Uniformly intensive burr shape, and part is presented in of uniform size, the diameter 150nm of polyaniline nano-line, nanowire surface
There are also tiny gaps at polyaniline nano-line center.Tetraphenylporphyrin tetrasulfonic acid (TPPS) is crosslinked the three-dimensional netted of polyaniline gel
Structure is conducive to the quick transmission of electronics, and the surface texture of burr shape increases the specific surface area of material, polyaniline can be improved and receive
The electro-chemical activity site of rice noodles.Polyaniline gel after freeze-drying is measured into its conductivity height by four probe resistance rate testers
Up to 0.32S/cm.
Embodiment 3
The aniline of 6mmol and 5mmol tetraphenylporphyrin tetrasulfonic acid (TPPS) are dissolved in 4mL distilled water, are stirred by ultrasonic
30min makes it sufficiently dissolve mixing, then places it in 4 DEG C of ice-water baths；The ammonium persulfate of 5mmol is dissolved in 3mL distilled water,
It is subsequently placed in 4 DEG C of ice-water baths；It will finally rapidly join dissolved with the solution of ammonium persulfate dissolved with four sulphur of aniline and tetraphenylporphyrin
Reaction 36h is stood in the solution of sour (TPPS), after ultrasonic 30s, is formed polyaniline gel, is then washed with distilled water 2-3 times；It will
The polyaniline gel of above-mentioned preparation is freeze-dried to obtain product.Electrically conductive polyaniline gel obtained is passed through into sem analysis, such as Fig. 3
Shown, gel is still the three-dimensional structure being made of nano wire.Polyaniline gel after freeze-drying is surveyed by four probe resistance rates
It is 0.31S/cm that examination instrument, which measures its conductivity,.
Embodiment 4
The preparation of polyaniline gel electrode: carbon paper is dried for standby after distilled water and ethyl alcohol rinse 3~5 times first.So
Afterwards by the electrically conductive polyaniline gel that embodiment 1 and embodiment 2 the synthesize carbon paper that is uniformly spun on that treated respectively, coating layer thickness
It is 30 μm, electrode is made in 60 DEG C of dryings of vacuum for 24 hours.
Polyaniline gel electrode electro Chemical performance test: the H of 1M is configured2SO4Solution is as electrolyte, with 5,10,20,50,
100 and 200mV/s's sweeps speed, tests polyaniline gel electricity by CHI 660E electrochemical workstation at voltage -0.2-0.8V
The cyclic voltammetric of pole；Polyaniline gel electrode is tested under current density 0.5,1,2,5 and 10A/g under different current densities
Capacitor.By experimental result, it can be seen that, New Polyaniline gel electrode shows good redox peaks (Fig. 4),
Its capacitor shows good high rate performance (Fig. 5, Fig. 6) still up to 187F/g under the high current of 10A/g.Impedance spectrum is aobvious
Show that polyaniline gel has excellent electronics and ionic conductivity (Fig. 7).This is for it in novel energy-storing electronic product
Using with important value and significance.
Nanometer threadiness electrically conductive polyaniline gel in the present invention can be achieved according to the adjustment that summary of the invention carries out technological parameter
Preparation, and show the performance almost the same with above-described embodiment.Illustrative description is done to the present invention above, it should say
It is bright, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art
The equivalent replacement of creative work can not be spent to each fall within protection scope of the present invention.
Claims (10)
1. a kind of nanometer of linear electrically conductive polyaniline gel, it is characterised in that: make crosslinking agent and doping with tetraphenylporphyrin tetrasulfonic acid
Agent is crosslinked a plurality of polyaniline molecule chain using polybasic sulfoacid and protonic acid doping synthesizes nanometer threadiness polyaniline gel, polyaniline
The tridimensional network that the braiding that is cross-linked with each other, interts and tangles between nano wire is constituted, polyaniline nano-line surface present uniform
Intensive burr shape, there are tiny gaps at part polyaniline nano-line center.
2. a kind of nanometer according to claim 1 linear electrically conductive polyaniline gel, it is characterised in that: the polyaniline is received
Rice noodles are of uniform size, diameter 120-180nm.
3. the preparation method of a kind of nanometer of linear electrically conductive polyaniline gel, it is characterised in that: the following steps are included:
(1) tetraphenylporphyrin tetrasulfonic acid and aniline are dispersed in distilled water, ice-water bath is carried out after ultrasonic agitation；Wherein four
The dosage of phenyl porphyrin tetrasulfonic acid is 0.1-5 molar part, and the dosage of aniline is 2-6 molar part；
(2) ammonium persulfate is dispersed in distilled water, then carries out ice-water bath；The wherein quality and step of ammonium persulfate
(1) the aniline equimolar ratio in；
(3) solution that step (2) obtains being added in the solution that step (1) obtains, standing after stirring keeps aniline polymerization complete,
It washs and is freeze-dried to obtain nanometer threadiness electrically conductive polyaniline gel.
4. the preparation method of a kind of nanometer according to claim 3 linear electrically conductive polyaniline gel, it is characterised in that: above-mentioned
The volume of distilled water is 1-4 parts by volume in step (1), and the ultrasonic agitation time is 30min, and the temperature of ice-water bath is 0-4 DEG C.
5. the preparation method of a kind of nanometer according to claim 3 linear electrically conductive polyaniline gel, it is characterised in that: above-mentioned
The volume of distilled water is 0.5~3 parts by volume in step (2), and the temperature of ice-water bath is 0-4 DEG C.
6. the preparation method of a kind of nanometer according to claim 3 linear electrically conductive polyaniline gel, it is characterised in that: above-mentioned
Mixing time is 1~60s in step (3), and time of repose is 12~48h, and sublimation drying is 12~48h.
7. the preparation method of a kind of nanometer of linear electrically conductive polyaniline gel electrode, it is characterised in that: the following steps are included:
(1) tetraphenylporphyrin tetrasulfonic acid and aniline are dispersed in distilled water, ice-water bath is carried out after ultrasonic agitation；Wherein four
The dosage of phenyl porphyrin tetrasulfonic acid is 0.1-5 molar part, and the dosage of aniline is 2-6 molar part；
(2) ammonium persulfate is dispersed in distilled water, then carries out ice-water bath；The wherein quality and step of ammonium persulfate
(1) the aniline equimolar ratio in；
(3) solution that step (2) obtains being added in the solution that step (1) obtains, standing after stirring keeps aniline polymerization complete,
It washs and is freeze-dried to obtain nanometer threadiness electrically conductive polyaniline gel；
(4) carbon paper is dried after distilled water and ethyl alcohol distinguish repeated flushing, the nanometer that then step (3) is prepared is linear
Electrically conductive polyaniline gel is uniformly spun on above-mentioned carbon paper, and nanometer threadiness electrically conductive polyaniline gel electricity is made by being dried in vacuo
Pole.
8. the preparation method of a kind of nanometer according to claim 7 linear electrically conductive polyaniline gel electrode, it is characterised in that:
The volume of distilled water is 1-4 parts by volume in above-mentioned steps (1), and the ultrasonic agitation time is 30min, and the temperature of ice-water bath is 0-4 DEG C；
The volume of distilled water is 0.5~3 parts by volume in above-mentioned steps (2), and the temperature of ice-water bath is 0-4 DEG C；Stirring in above-mentioned steps (3)
Time is 1~60s, and time of repose is 12~48h, and sublimation drying is 12~48h；Above-mentioned steps are spun on described in (4)
Nanometer threadiness electrically conductive polyaniline gel on carbon paper with a thickness of 20-50 μm.
9. application of a kind of nanometer of linear electrically conductive polyaniline gel electrode in supercapacitor, it is characterised in that: use the time
Voltage method tests capacitor of the polyaniline gel electrode under different current densities, and when current density is 0.5A/g, capacitor is
300-350F/g, when current density is 10A/g, capacitor is still up to 180-190F/g.
10. application of a kind of nanometer of linear electrically conductive polyaniline gel in supercapacitor, it is characterised in that: lead nanometer threadiness
Conducting polyaniline gel is uniformly spun on above-mentioned carbon paper, and nanometer threadiness electrically conductive polyaniline gel electrode is made by being dried in vacuo,
This nanometer threadiness electrically conductive polyaniline gel electrode is applied in supercapacitor, tests polyaniline gel using time voltage method
Capacitor of the electrode under different current densities, when current density is 0.5A/g, capacitor is 300-350F/g, is in current density
When 10A/g, capacitor is still up to 180-190F/g.
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|---|---|---|---|---|
| WO2006125825A2 (en) * | 2005-05-27 | 2006-11-30 | The Provost Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Method of forming conducting nanowires |
| CN105295038A (en) * | 2015-11-05 | 2016-02-03 | 天津大学 | Conductive polyaniline gel preparation methods and application of same to supercapacitor |
| CN106653386A (en) * | 2016-12-02 | 2017-05-10 | 哈尔滨工业大学（威海） | Carbon-polyaniline supercapacitor and preparation method thereof |
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2017
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| WO2006125825A2 (en) * | 2005-05-27 | 2006-11-30 | The Provost Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Method of forming conducting nanowires |
| CN105295038A (en) * | 2015-11-05 | 2016-02-03 | 天津大学 | Conductive polyaniline gel preparation methods and application of same to supercapacitor |
| CN106653386A (en) * | 2016-12-02 | 2017-05-10 | 哈尔滨工业大学（威海） | Carbon-polyaniline supercapacitor and preparation method thereof |
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| TSUKASA ET AL.: "New Morphology-Controlled Poly(aniline)Synthesis Using Anionic Porphyrin Aggregate as a Template and Proton-Driven Structural Changes in the Porphytin Aggregate", 《BULL.CHEM.SOC.JPN.》 * |
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