CN105295038B - The preparation method of electrically conductive polyaniline gel and its application in ultracapacitor - Google Patents
The preparation method of electrically conductive polyaniline gel and its application in ultracapacitor Download PDFInfo
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- CN105295038B CN105295038B CN201510744209.3A CN201510744209A CN105295038B CN 105295038 B CN105295038 B CN 105295038B CN 201510744209 A CN201510744209 A CN 201510744209A CN 105295038 B CN105295038 B CN 105295038B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007639 printing Methods 0.000 claims abstract description 28
- 239000005457 ice water Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical compound NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 abstract description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 16
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 10
- 238000012857 repacking Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004215 lattice model Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- -1 phosphoric acid small molecule Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to conductive polymer gel, disclose the preparation method of electrically conductive polyaniline gel and its application in ultracapacitor, one of preparation method is that ammonium persulfate solution is added into aniline and ATMP solution, and reaction makes aniline polymerization completely in ice-water bath, is washed out freeze-drying and produces；The two of preparation method are to add aniline and ATMP solution in the shower nozzle A of 3D printer, ammonium persulfate solution are added in the shower nozzle B of 3D printer, by shower nozzle A and shower nozzle B, printing alternate reacts to be formed in same point in 0~4 DEG C of environment；The gel that above two method is prepared can be uniformly spun on the carbon paper after processing, and electrically conductive polyaniline gel electrode is made in vacuum drying.Present invention, avoiding the introducing of non-conductive polymer, electric conductivity is improved, the more excellent electrically conductive polyaniline gel of obtained performance, it is used as electrode material, is that polyaniline gel is applied directly on collector, reduces the amount of inert matter in electrode.
Description
Technical field
It is to be related to polynary phosphoric acid small molecule crosslinking specifically the present invention relates to the preparation method of conductive polymer gel
Polyaniline synthesizes the preparation method and stored energy application of electrically conductive polyaniline gel.
Background technology
In recent years, conducting polymer due to being widely used in the new energy such as ultracapacitor and lithium ion battery equipment and
Of great interest, it is not only cheap, and environmental stability is good, and also certain electronic conduction ability.However, with
The development of various flexible and high-power energy device, the relatively low electrical conductivity of conventional conductive polymer material and poor processability
Usually limit its application on high-performance equipment.Therefore, research electric conductivity and the excellent novel conductive of processing characteristics are poly-
Compound material tool is of great significance.
Conductive polymer gel is while having the polymeric material of gel and organic conductor excellent properties concurrently.Especially nanometer
The conductive polymer gel of structure, with high surface area and three-dimensional continuous conductive network, is used as ultracapacitor
Electrode, or binding agent and conductive agent in conventional lithium ion battery electrode are substituted, electrolyte can enter its internal micro-nano hole
Road, is conducive to fully contacting for electrode material and electrolyte solution, relative to traditional two-dimensional film there is shorter ion to expand
Path is dissipated, chemical property of the electrode material in high power charging-discharging can be improved, and the conductive network of connection carries for electronics
Quick transmission channel has been supplied, the fast charging and discharging performance of electrode material can be achieved.In addition, conductive polymer gel have it is excellent
Machinability, can be made film or other desired shape, this causes it ultra-thin soft by modes such as casting, spraying or printings
Property electrode in terms of have huge application value and potentiality.Although conductive polymer gel has numerous excellent properties, mesh
Preceding conductive polymer gel is still to be made by the way that conducting polymer and non-conductive polymer are blended, conduction prepared by this method
Although polymer can influence the biography of conducting polymer materials electronics with good mechanical performance, the incorporation of non-conductive polymer
It is defeated, the specific surface area of gel is reduced, so as to influence its chemical property.Based on this, the new system of conductive polymer gel is studied
Preparation Method is just significant.
The content of the invention
The present invention is to solve current conductive polymer gel influences its electricity due to the incorporation of non-conductive polymer
The technical problem of chemical property there is provided a kind of preparation method of electrically conductive polyaniline gel and its application in ultracapacitor,
Using ATMP (ATMP) as the crosslinking agent of synthesis electrically conductive polyaniline gel, itself and polyaniline point are on the one hand utilized
The three-dimensional gel structure that subchain is cross-linked to form, it is to avoid the introducing of non-conductive polymer, on the other hand passes through proton doping and improves
The electric conductivity of polyaniline gel, so that the more excellent electrically conductive polyaniline gel of performance is made.
Meanwhile, the polyaniline gel of the invention being crosslinked using ATMP is electrode material, the electric capacity as electrode of super capacitor
And performance study.The traditional preparation methods of electrode of super capacitor are coated after mixing electrode material, conductive agent and adhesive
It is made on a current collector, the energy density of electrode can be reduced to a certain extent by introducing conductive agent and adhesive.The present invention be by
Polyaniline gel is applied directly on collector, reduces the amount of inert matter in electrode.
In order to solve the above-mentioned technical problem, the present invention is achieved by following technical scheme：
A kind of preparation method of electrically conductive polyaniline gel, this method is followed the steps below：
(1) 2~6mmol aniline and 1~5mmol aminotrimethylene phosphoric acid are dissolved in 1~4mL distilled water, it is placed in 0~
In 4 DEG C of ice-water baths；
(2) 0.1~0.5g ammonium persulfates are dissolved in 0.5~3mL distilled water, be placed in 0~4 DEG C of ice-water bath；
(3) solution for configuring step (2) is added in the solution of step (1) configuration, and reaction is stood after ultrasound gathers aniline
Close complete, then distill water washing, freeze-drying produces electrically conductive polyaniline gel.
A kind of preparation method of electrically conductive polyaniline gel, this method is followed the steps below：
(1) 2~6mmol aniline and 1~5mmol aminotrimethylene phosphoric acid are dissolved in 1~4mL distilled water, and are added to
In the shower nozzle A of 3D printer；
(2) 0.1~0.5g ammonium persulfates are dissolved in 0.5~3mL distilled water, and be added in the shower nozzle B of 3D printer；
(3) by the shower nozzle A and shower nozzle B of 3D printer, printing alternate reacts to be formed in same point in 0~4 DEG C of environment
5~10s, shower nozzle A and shower nozzle B is spaced between electrically conductive polyaniline gel, and shower nozzle A and each printing alternates of shower nozzle B to print every time
Extrusion capacity be 0.50~2 μ L.
A kind of electrically conductive polyaniline gel, is made by one of above two preparation method.
A kind of preparation method of electrically conductive polyaniline gel electrode, after carbon paper is rinsed into 3~5 times repeatedly through distilled water and ethanol
Dry for standby, is then uniformly spun on the carbon paper after processing by electrically conductive polyaniline gel made from one of above two preparation method
On, finally it is dried in vacuo and electrically conductive polyaniline gel electrode is made.
The beneficial effects of the invention are as follows：
The present invention makees crosslinking agent and dopant with ATMP, is mixed using a plurality of polyaniline molecule chain of polynary phosphate cross and proton
Heterozygosis is into polyaniline gel, and it is free of non-conductive polymer, and with big specific surface area, excellent electric conductivity and good electricity
Chemical property.Preparation method of the present invention is quick and easy, non-environmental-pollution, is adapted to industrialized production.The present invention is made
Standby electrically conductive polyaniline gel electrode can be used for ultracapacitor, at room temperature, using three-electrode system in 1.0M H2SO4In
Electro-chemical test is carried out, the cyclic voltammetric result in the case where 10~200mv/s sweeps speed shows that electrically conductive polyaniline gel electrode has substantially
Redox property, show the feasibility as electrode of super capacitor；Polyaniline is tested using time voltage method to coagulate
Electric capacity of the gel electrode under different current densities, shows that it has excellent high rate performance and cycle life, can meet super capacitor
Requirement of the device to high performance electrode material.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of electrically conductive polyaniline gel prepared by embodiment 1；
Fig. 2 is stereoscan photograph (a and b) of the electrically conductive polyaniline gel of the preparation of embodiment 2 under different resolution, with
And its specific surface area and graph of pore diameter distribution (c)；
Fig. 3 is the stereoscan photograph of electrically conductive polyaniline gel prepared by embodiment 3；
Fig. 4 is that embodiment 4-6 prepares shower nozzle (a) and process schematic (b) used in electrically conductive polyaniline gel；
Fig. 5 is the digital photograph of three-dimensional conductive polyaniline gel array prepared by embodiment 4；
Fig. 6 is the digital photograph that embodiment 5 prepares " TJU " alphabetical printed words electrically conductive polyaniline gel；
Fig. 7 is the cyclic voltammetry curve of electrically conductive polyaniline gel electrode prepared by embodiment 6；
Fig. 8 is time-measuring electric potential (E-t) curve of electrically conductive polyaniline gel electrode prepared by embodiment 6；
Fig. 9 is the cycle life curve of electrically conductive polyaniline gel electrode prepared by embodiment 6；
Figure 10 is the impedance spectra of electrically conductive polyaniline gel electrode prepared by embodiment 6.
Embodiment
Below by specific embodiment, the present invention is described in further detail, and following examples can make this specialty
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
2mmol aniline and 1mmol ATMP are dissolved in 1mL distilled water, it is mixed that ultrasonic agitation 30min makes it fully dissolve
Close, be then placed on 0 DEG C of ice-water bath；0.1g ammonium persulfate is dissolved in 0.5mL distilled water, 0 DEG C of ice-water bath is subsequently placed in
In；Finally the solution dissolved with ammonium persulfate is rapidly joined in the solution dissolved with aniline and ATMP, reaction is stood after ultrasonic 10s
10min, forms polyaniline gel, then uses distillation water washing 2-3 times；The polyaniline gel freeze-drying of above-mentioned preparation is obtained
Product.Obtained electrically conductive polyaniline gel is analyzed by SEM (SEM), as shown in Figure 1, it can be seen that gel
It is connected with each other between the three-dimensional network loose structure being made up of nanometer sheet, nanometer sheet.Polyaniline gel after will be lyophilized passes through four
Probe resistance rate tester measures its electrical conductivity for 0.31S/cm, the polyaniline gel prepared far above conventional method.
Embodiment 2
4mmol aniline and 3mmol ATMP are dissolved in 2mL distilled water, it is mixed that ultrasonic agitation 30min makes it fully dissolve
Close, be then placed on 2 DEG C of ice-water baths；0.25g ammonium persulfate is dissolved in 1mL distilled water, 2 DEG C of ice-water baths are subsequently placed in
In；Finally the solution dissolved with ammonium persulfate is rapidly joined in the solution dissolved with aniline and ATMP, reaction is stood after ultrasonic 15s
30min, forms polyaniline gel, then uses distillation water washing 2-3 times；The polyaniline gel freeze-drying of above-mentioned preparation is obtained
Product.Obtained electrically conductive polyaniline gel is analyzed by SEM and specific surface area (BET), as shown in Fig. 2 polyaniline gel by
It is uniformly distributed on the three-dimensional network loose structure of the nanometer sheet composition of interconnection, nanometer sheet thickness about 60nm, and nanometer sheet
A large amount of micropores.The specific surface area of made polyaniline is 37.2m2/ g, average pore size is 324.8nm.Polyaniline after will be lyophilized coagulates
Glue measures its electrical conductivity up to 0.37S/cm by four probe resistance rate testers.
Embodiment 3
6mmol aniline and 5mmol ATMP are dissolved in 4mL distilled water, it is mixed that ultrasonic agitation 30min makes it fully dissolve
Close, be then placed on 4 DEG C of ice-water baths；0.5g ammonium persulfate is dissolved in 3mL distilled water, is subsequently placed in 4 DEG C of ice-water baths；
Finally the solution dissolved with ammonium persulfate is rapidly joined in the solution dissolved with aniline and ATMP, reaction is stood after ultrasonic 30s
60min, forms polyaniline gel, then uses distillation water washing 2-3 times；The polyaniline gel freeze-drying of above-mentioned preparation is obtained
Product.By obtained electrically conductive polyaniline gel by sem analysis, as shown in figure 3, gel is still the three-dimensional being made up of nanometer sheet
Structure.Polyaniline gel after will be lyophilized measures its electrical conductivity for 0.35S/cm by four probe resistance rate testers.
Embodiment 4
First by prusa i3mendel 3D printers by increasing by two timing belts, two stepper motors and a spray
Melting extrusion type shower nozzle A and B, are then substituted for the solution extrusion type as shown in Fig. 4 (a) by head repacking nozzle printing machine in pairs again
Shower nozzle, polyaniline gel is prepared for printing；2mmol aniline and 1mmol ATMP are dissolved in 1mL distilled water, are then added to
In the shower nozzle A of 3D printer after repacking；0.1g ammonium persulfates are dissolved in 0.5mL distilled water, are then added to after repacking
In the shower nozzle B of 3D printer；Printing head A and B printing alternates in 0 DEG C of environment are controlled by Repetier-Host softwares
React to form gel in same point, printing flow signal such as Fig. 4 (b), the interval time of each printing alternates of printing head A and B
For 5s, each μ L of extrusion capacity 0.5.Blackish green polyaniline gel, four probe resistance rate testers are obtained by printing alternate
Its electrical conductivity is measured for 0.3S/cm.
Embodiment 5
First by prusa i3mendel 3D printers by increasing by two timing belts, two stepper motors and a spray
Melting extrusion type shower nozzle A and B, are then substituted for the solution extrusion type as shown in Fig. 4 (a) by head repacking nozzle printing machine in pairs again
Shower nozzle, polyaniline gel is prepared for printing；4mmol aniline and 3mmol ATMP are dissolved in 2mL distilled water, are then added to
In the shower nozzle A of 3D printer after repacking；0.25g ammonium persulfates are dissolved in 1mL distilled water, the 3D after repacking is then added to
In the shower nozzle B of printer；The lattice model of one 5 × 5 using 3d max Software for Design, passes through Repetier-Host softwares
Control printing head A and B printing alternates in 2 DEG C of environment react to form gel in same point, printing flow signal such as Fig. 4 b,
The interval time of each printing alternates of printing head A and B is 7s, each μ L of extrusion capacity 1.Obtained by the printing alternates of 20 times
The polyaniline gel array consistent with built lattice model (height about 1.5cm), as shown in Figure 5.Using four probe resistance rates
Tester measures its electrical conductivity for 0.38S/cm.
Embodiment 6
First by prusa i3mendel 3D printers by increasing by two timing belts, two stepper motors and a spray
Melting extrusion type shower nozzle A and B, are then substituted for the solution extrusion type as shown in Fig. 4 (a) by head repacking nozzle printing machine in pairs again
Shower nozzle, polyaniline gel is prepared for printing；6mmol aniline and 5mmol ATMP are dissolved in 4mL distilled water, are then added to
In the shower nozzle A of 3D printer after repacking；0.5g ammonium persulfates are dissolved in 3mL distilled water, the 3D after repacking is then added to
In the shower nozzle B of printer；One " TJU " mode letters using 3d max Software for Design, pass through Repetier-Host software controls
Printing head A and B processed printing alternates in 4 DEG C of environment react to form gel in same point, and printing head A and B replace every time
Time is 10s, each μ L of extrusion capacity 2.Height about 0.5cm polyaniline gel letter is formd by the printing alternate of 5 times
Printed words, as shown in Figure 6.Four probe resistance rate testers are used to measure its electrical conductivity for 0.33S/cm.
Embodiment 7
The preparation of polyaniline gel electrode：First by carbon paper after distilled water and alcohol flushing 3~5 times dry for standby.So
The electrically conductive polyaniline gel for afterwards synthesizing embodiment 2 and embodiment 5 is uniformly spun on the carbon paper after processing respectively, coating layer thickness
About 30 μm, electrode is made in the dry 24h of 60 DEG C of vacuum.
Polyaniline gel electrode electro Chemical performance test：Configure 1M H2SO4Solution is as electrolyte, with 10,20,50,
100 and 200mV/s's sweeps speed, and polyaniline gel electricity is tested by CHI 660E electrochemical workstations under voltage -0.2-0.8V
The cyclic voltammetric of pole；Electricity of the polyaniline gel electrode under different current densities is tested under current density 0.5,1,2 and 5A/g
Hold；The cyclical stability of polyaniline gel electrode is tested under 2A/g current density.By experimental result it can be seen that, it is new poly-
Aniline gel electrode shows good redox peaks (Fig. 7), and its electric capacity is still up to 280F/ under 5A/g high current
G, shows good high rate performance (Fig. 8).Can be seen that polyaniline gel electrode by circulation figure has good circulation steady
Qualitative, its capacity is maintained at 320F/g after 2000 circulations, and capability retention is up to 92% (Fig. 9).Impedance spectrum shows polyphenyl
Amine gel has excellent electronics and ionic conductivity (Figure 10).This has for its application in novel energy-storing electronic product
There is important value and significance.
Although the preferred embodiments of the present invention are described above in conjunction with accompanying drawing, the invention is not limited in upper
The embodiment stated, above-mentioned embodiment is only schematical, be not it is restricted, this area it is common
Technical staff in the case of present inventive concept and scope of the claimed protection is not departed from, may be used also under the enlightenment of the present invention
To make the specific conversion of many forms, these are belonged within protection scope of the present invention.
Claims (4)
1. a kind of preparation method of electrically conductive polyaniline gel, it is characterised in that this method is followed the steps below：
(1) 2~6mmol aniline and 1~5mmol aminotrimethylene phosphoric acid are dissolved in 1~4mL distilled water, are placed in 0~4 DEG C
In ice-water bath；
(2) 0.1~0.5g ammonium persulfates are dissolved in 0.5~3mL distilled water, be placed in 0~4 DEG C of ice-water bath；
(3) solution for configuring step (2) is added in the solution of step (1) configuration, and reaction is stood after ultrasound makes aniline polymerization complete
Entirely, water washing is then distilled, freeze-drying produces electrically conductive polyaniline gel.
2. a kind of preparation method of electrically conductive polyaniline gel, it is characterised in that this method is followed the steps below：
(1) 2~6mmol aniline and 1~5mmol aminotrimethylene phosphoric acid are dissolved in 1~4mL distilled water, and are added to 3D and beaten
In the shower nozzle A of print machine；
(2) 0.1~0.5g ammonium persulfates are dissolved in 0.5~3mL distilled water, and be added in the shower nozzle B of 3D printer；
(3) by the shower nozzle A and shower nozzle B of 3D printer, printing alternate reacts to form conduction in same point in 0~4 DEG C of environment
What interval 5~10s, shower nozzle A and shower nozzle B were printed every time between polyaniline gel, and shower nozzle A and each printing alternates of shower nozzle B squeezes
Output is 0.50~2 μ L.
3. a kind of electrically conductive polyaniline gel, it is characterised in that be made by the preparation method of claim 1 or 2.
4. a kind of preparation method of electrically conductive polyaniline gel electrode, it is characterised in that rush carbon paper repeatedly through distilled water and ethanol
Dry for standby after 3~5 times is washed, then the electrically conductive polyaniline gel prepared by claim 1 or 2 is uniformly spun on after processing
On carbon paper, finally it is dried in vacuo and electrically conductive polyaniline gel electrode is made.
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| CN109320717A (en) * | 2017-07-31 | 2019-02-12 | 天津大学 | The preparation method of a kind of nanometer of linear electrically conductive polyaniline gel and its application in supercapacitor |
| CN110299251A (en) * | 2018-03-23 | 2019-10-01 | 中国科学技术大学 | The preparation method of electrically conductive polyaniline hydrogel and stretchable supercapacitor |
| CN109148170A (en) * | 2018-08-23 | 2019-01-04 | 天津大学 | A kind of preparation method and application of three-dimensional porous manganese tetraoxide/polyaniline plural gel electrode |
| CN110060816B (en) * | 2019-04-23 | 2021-04-20 | 西北工业大学深圳研究院 | Method for local in-situ electropolymerization of conductive polymer by 3D printing |
| CN112920406B (en) * | 2021-02-08 | 2022-04-19 | 中国科学技术大学 | Flexible self-supporting anisotropic electrochromic polyaniline film and preparation method thereof, and electrochromic device |
| CN112980276A (en) * | 2021-04-16 | 2021-06-18 | 浙江凯色丽科技发展有限公司 | Attapulgite-mica-based conductive anticorrosive paint and preparation method thereof |
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| CN101851398A (en) * | 2010-05-12 | 2010-10-06 | 北京理工大学 | Conductive polymer aerogel and preparation method thereof |
| CN102702517A (en) * | 2012-06-08 | 2012-10-03 | 武汉工程大学 | Preparation method of sulfonated grapheme/polyaniline composite |
| CN103205914A (en) * | 2013-04-08 | 2013-07-17 | 广东轻工职业技术学院 | Conductive polymer composite conductive paper and preparation method and application thereof |
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2015
- 2015-11-05 CN CN201510744209.3A patent/CN105295038B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851398A (en) * | 2010-05-12 | 2010-10-06 | 北京理工大学 | Conductive polymer aerogel and preparation method thereof |
| CN102702517A (en) * | 2012-06-08 | 2012-10-03 | 武汉工程大学 | Preparation method of sulfonated grapheme/polyaniline composite |
| CN103205914A (en) * | 2013-04-08 | 2013-07-17 | 广东轻工职业技术学院 | Conductive polymer composite conductive paper and preparation method and application thereof |
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| Rapid synthesis of hierarchiacl nanostructured Polyaniline hydrogel for high power density energy storage application and three-dimensional multilayers printing;PengDou et al;《J.Mater.Sci.》;20160126;4274-4282 * |
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