CN102952268B - Single cis-conformation polyaniline conducting polymer material and preparation method thereof - Google Patents
Single cis-conformation polyaniline conducting polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN102952268B CN102952268B CN201210420329.4A CN201210420329A CN102952268B CN 102952268 B CN102952268 B CN 102952268B CN 201210420329 A CN201210420329 A CN 201210420329A CN 102952268 B CN102952268 B CN 102952268B
- Authority
- CN
- China
- Prior art keywords
- polymer material
- conductive polymer
- polyaniline
- conformation
- polyaniline conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a single cis-conformation polyaniline conducting polymer material and a preparation method thereof. The benzene rings in the single cis-conformation polyaniline conducting polymer material are connected in a cis-spiral direction; the molecular weight is 4500-30000; and an included angle of two benzene rings and a nitrogen atom is 135-175 DEG. The material is prepared by an electrochemical polymerization method. Compared with existing polyaniline materials, the polyaniline conducting polymer material provided by the invention has lower charge transfer resistance, higher apparent diffusion coefficient, better hydrophilicity, higher ion exchange capacity, super high stability, and excellent super-capacitor performance and sensor performance.
Description
Technical field
The invention belongs to conducting polymer composite technical field, be specifically related to single cisoid conformation polyaniline
conducting polymermaterial and preparation method thereof.
Background technology
In recent years, along with nanometer science and technology is in the deep development in each field, the conducting polymer composite (as polyaniline, polypyrrole etc.) of one dimension Nano structure had caused investigator's very big interest.It has small aperture size, physical property that narrow pore size distribution and specific surface area etc. is excellent, there is again the structure of nano material uniqueness, obtained good application at numerous areas such as molecular circuit, molecular memory equipment, opto-electronic device, modified electrode, sensor, advanced composite material, life science and drug targeting control releases.
Polyaniline is as one of Typical Representative of conducting polymer composite, there is raw material and be easy to get, synthesize easy, excellent electrical property and chemical property, especially also there is stable chemical nature and eco-friendly feature, in conduction high polymer, have very important status, be the study hotspot in conducting polymer composite field always.It has broad application prospects at aspects such as ultracapacitor, chemical power source, antistatic, electrochromism, water wetted material, electromagnetic shielding and biochemical sensors.
The preparation method of existing polyaniline nano structure has template, self-assembly method, electrospinning weave, interfacial polymerization, surfactant method and electrochemical method etc.Wherein because of simple to operate and p-poly-phenyl amine pattern controllability, extremely numerous scholars and slip-stick artist favor electrochemical method by force.
Electrochemical method mainly comprises: cyclic voltammetry [J. Electroanal. Chem. 568 (2004): 189], potentiostatic method [J. Electroanal. Chem. 242 (1988): 243] and galvanostatic method [J. Electroanal. Chem. 177 (1984): 293], it is the polyaniline that mixes conformation that these three kinds of methods make polyaniline, pattern is random particle or sheet, and its loading capacity is little, less and cyclical stability is poor than electric capacity; Pulse current method [Thin Solid Films 450 (2004): 233, and Synth. Met. 157 (2007): 98] and unipolar pulse method [Synth. Met. 162 (2012): 107, and Chinese patent CN101942090A], these two kinds of methods make polyaniline and are similarly mixing conformation polyaniline, but pattern is well-regulated nanofiber and nanometer rod, and its chemical property makes polyaniline higher than first three methods.
The research of the chemistry that the current conformational isomerism about polyaniline and its conformation cause and the theory and technology of change in physical is few, can improve from molecule rank the various performances of polyaniline by the research of conformational isomerism, make itself intrinsic performance obtain collaborative perform to ultimate attainment.Polyaniline isomeric form has directly determined electrical attributes, optical properties, magnetic properties, structure attribute and the mechanical attributes of polyaniline itself.Polyaniline conformational isomerism mainly comprises position isomerism, cis/trans isomery and rotational isomeric three types.Therefore in order to improve to greatest extent the performance of polyaniline self, we consider by the polyaniline conductive polymer material of synthetic single conformation, or have the polyaniline of a small amount of other isomeric form of doping to make its essential attribute obtain surprising raising.
Summary of the invention
The object of the present invention is to provide a kind of single cisoid conformation polyaniline conductive polymer material, be characterized in that the structural formula of described material is:
Wherein n=15-110, and in described material, phenyl ring is that the cis hand of spiral connects, and molecular weight is that 4500～30000, two phenyl ring and nitrogen-atoms angle are: 135 °～175 °.
Single cisoid conformation polyaniline conductive polymer material of the present invention has good ultracapacitor performance, at the ratio electric capacity of material described in acidic medium at 900～1200Fg
-1between; And the cyclical stability of described single cisoid conformation polyaniline conductive polymer material is very good, after 2000 times discharge and recharge specific storage still remain on original 85% or more than, preferably remain on original 95% or more than.
The present invention also provides a kind of preparation method of single cisoid conformation polyaniline conductive polymer material, said method comprising the steps of:
(1) aniline monomer and sulfuric acid are added in water, stir the sulphuric acid soln of the aniline that forms homogeneous transparent;
(2) in three-electrode system, the sulphuric acid soln of aniline is added in electrochemical reaction cell, at the enterprising horizontal pulse electropolymerization of working electrode, after polymerization, cleans with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material;
It is characterized in that: the pulse signal of described pulse is: pulsed voltage: 0.8～1.1 V(is with respect to saturated calomel electrode), pulse ETAD expected time of arrival and departure is 0.001s～0.01s, and controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:100～1:10.
Preferably, electrochemical reaction of the present invention is carried out at the temperature of 0-25 DEG C, more preferably at the temperature of 0 DEG C of left and right, reacts.
Present inventor is on the basis of lot of experiments, the developmental process of polyaniline in electrochemical reaction process has been carried out to trickle control, find pulse ETAD expected time of arrival and departure to be controlled at the very short time, for example 0.001s～0.01s, and pulse break make ratio is controlled within the scope of 1:100～1:10, the polyaniline macromolecular material obtaining presents single cisoid conformation structure, and phenyl ring is wherein the cis hand of spiral and connects as shown in Figure 1, and two phenyl ring and nitrogen-atoms angle are: 135 °～175 °.Compared with current mixing conformation polyaniline conductive polymer material, single cisoid conformation polyaniline conductive polymer material of the present invention has good ultracapacitor and sensor performance, and charge transfer resistance is lower, wetting ability and wettability is better and electrochemical stability is better.Material disclosed by the invention has also been filled up the blank of polyaniline in the controlled one-tenth long side of conformation.
Tool of the present invention has the following advantages:
(1) single cisoid conformation polyaniline conductive polymer material of the present invention and preparation method thereof has been filled up the blank of polyaniline in the controlled one-tenth long side of conformation, has really realized the conformation of macromolecular material growth controlled.
(2) material of the present invention, compared with current polyaniline material, has good ultracapacitor and sensor performance, and has low charge transfer resistance, better wetting ability and wettability and superpower electrochemical stability.
(3) the single cisoid conformation polyaniline conductive polymer material Ascorbic Acid that prepared by the present invention has good electrocatalysis characteristic, has higher sensitivity, good linearity range and satisfactory stability.
Brief description of the drawings
Fig. 1 is the cis hand of spiral connection diagram of phenyl ring in single cisoid conformation polyaniline conductive polymer material of the present invention.
Embodiment
The present invention is further described in detail the specific embodiment of the present invention by the following specific embodiments.
embodiment 1
(1) aniline monomer of 9.3598 g is dissolved in the aqueous solution of 250 ml and is configured to the aniline-water solution A that volumetric molar concentration is 0.4 mol/L;
(2) vitriol oil of 51.083 g is dissolved in to the aqueous sulfuric acid B that is configured to 1 mol/L in the water of 500 ml;
(3) get 20 ml solution A and 20 ml solution B and insert in electrochemical reaction cell and stir, form the sulphuric acid soln of the aniline of homogeneous transparent.
(4) in three-electrode system, at 0 DEG C of temperature, at the enterprising horizontal pulse electropolymerization of working electrode.Pulse signal is set to: apply pulsed voltage: 0.9 V(is with respect to saturated calomel electrode), controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:90, and pulse ETAD expected time of arrival and departure is 0.001s, and pulse number is 200.
(5) after polymerization, clean with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material, its molecular weight is that 27900, two phenyl ring and nitrogen-atoms key key angle are: 170 °.
Under three-electrode system, the above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to super capacitor performance test in the sulphuric acid soln of 0.5 mol/L, it reaches 1180 F/g than electric capacity, discharges and recharges rear specific storage for 2000 times and remains on original 99%.
The above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to sensor performance test.In three-electrode system, polyaniline film cathode prepared by single cisoid conformation polyaniline conductive polymer material of the present invention is as working electrode, taking the sulphuric acid soln of 0.1 mol/L as supporting electrolyte, the xitix that drips successively different concns carries out cyclic voltammetry scan.In the concentration X of xitix is 1 μ mol/L～0.1 mol/L concentration range, oxidation peak current and concentration exist good linear relationship, and linear equation is Y=25.27X+50.93, and relation conefficient is R
2=0.9921, lowest detection is limited to 0.2 μ mol/L.
embodiment 2
(1) aniline monomer of 9.3598 g is dissolved in the aqueous solution of 250 ml and is configured to the aniline-water solution A that volumetric molar concentration is 0.4 mol/L;
(2) vitriol oil of 51.083 g is dissolved in to the aqueous sulfuric acid B that is configured to 1 mol/L in the water of 500 ml;
(3) get 20 ml solution A and 20 ml solution B and insert in electrochemical reaction cell and stir, form the sulphuric acid soln of the aniline of homogeneous transparent.
(4) in three-electrode system, at 0 DEG C of temperature, at the enterprising horizontal pulse electropolymerization of working electrode.Pulse signal is set to: apply pulsed voltage: 0.90 V(is with respect to saturated calomel electrode), controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:50, and pulse ETAD expected time of arrival and departure is 0.005s, and pulse number is 400.
(5) after polymerization, clean with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material, its molecular weight is that 18900, two phenyl ring and nitrogen-atoms key key angle are: 160 °.
Under three-electrode system, the single cisoid conformation polyaniline conductive polymer material preparing is carried out to super capacitor performance test in the sulphuric acid soln of 0.5 mol/L, it reaches 1020 F/g than electric capacity, discharges and recharges rear specific storage for 2000 times and remains on original 98%.
The single cisoid conformation polyaniline conductive polymer material preparing is carried out to sensor performance test.In three-electrode system, polyaniline film cathode prepared by single cisoid conformation polyaniline conductive polymer material of the present invention is as working electrode, taking the sulphuric acid soln of 0.1 mol/L as supporting electrolyte, the xitix that drips successively different concns carries out cyclic voltammetry scan.In the concentration X of xitix is 10 μ mol/L～0.1 mol/L concentration ranges, oxidation peak current and concentration exist good linear relationship, and linear equation is Y=29.38X+64.87, and relation conefficient is R
2=0.9935, lowest detection is limited to 1 μ mol/L.
embodiment 3
(1) aniline monomer of 9.3598 g is dissolved in the aqueous solution of 250 ml and is configured to the aniline-water solution A that volumetric molar concentration is 0.4 mol/L;
(2) vitriol oil of 51.083 g is dissolved in to the aqueous sulfuric acid B that is configured to 1 mol/L in the water of 500 ml;
(3) get 20 ml solution A and 20 ml solution B and insert in electrochemical reaction cell and stir, form the sulphuric acid soln of the aniline of homogeneous transparent.
(4) in three-electrode system, at 0 DEG C of temperature, at the enterprising horizontal pulse electropolymerization of working electrode.Pulse signal is set to: apply pulsed voltage: 0.9 V(is with respect to saturated calomel electrode), controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:10, and pulse ETAD expected time of arrival and departure is 0.01s, and pulse number is 500.
(5) after polymerization, clean with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material, its molecular weight is that 10010, two phenyl ring and nitrogen-atoms key key angle are: 140 °.
Under three-electrode system, the single cisoid conformation polyaniline conductive polymer material preparing is carried out to super capacitor performance test in the sulphuric acid soln of 0.5 mol/L, it reaches 954 F/g than electric capacity, discharges and recharges rear specific storage for 2000 times and remains on original 96%.
The single cisoid conformation polyaniline conductive polymer material preparing is carried out to sensor performance test.In three-electrode system, polyaniline film cathode prepared by single cisoid conformation polyaniline conductive polymer material just of the present invention is as working electrode, taking the sulphuric acid soln of 0.1 mol/L as supporting electrolyte, the xitix that drips successively different concns carries out cyclic voltammetry scan.In the concentration X of xitix is 35 μ mol/L～0.08 mol/L concentration ranges, oxidation peak current and concentration exist good linear relationship, and linear equation is Y=34.62X+85.28, and relation conefficient is R
2=0.9953, lowest detection is limited to 5 μ mol/L.
embodiment 4
(1) aniline monomer of 9.3598 g is dissolved in the aqueous solution of 250 ml and is configured to the aniline-water solution A that volumetric molar concentration is 0.4 mol/L;
(2) vitriol oil of 51.083 g is dissolved in to the aqueous sulfuric acid B that is configured to 1 mol/L in the water of 500 ml;
(3) get 20 ml solution A and 20 ml solution B and insert in electrochemical reaction cell and stir, form the sulphuric acid soln of the aniline of homogeneous transparent.
(4) in three-electrode system, at 10 DEG C of temperature, at the enterprising horizontal pulse electropolymerization of working electrode.Pulse signal is set to: apply pulsed voltage: 1.0 V(are with respect to saturated calomel electrode), controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:70, and pulse ETAD expected time of arrival and departure is 0.003s, and pulse number is 300.
(5) after polymerization, clean with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material, its molecular weight is that 22000, two phenyl ring and nitrogen-atoms key key angle are: 165 °.
Under three-electrode system, the above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to super capacitor performance test in the sulphuric acid soln of 0.5 mol/L, it reaches 986 F/g than electric capacity, discharges and recharges rear specific storage for 2000 times and remains on original 94%.
The above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to sensor performance test.In three-electrode system, polyaniline film cathode prepared by single cisoid conformation polyaniline conductive polymer material of the present invention is as working electrode, taking the sulphuric acid soln of 0.1 mol/L as supporting electrolyte, the xitix that drips successively different concns carries out cyclic voltammetry scan.In the concentration X of xitix is 1 μ mol/L～0.1 mol/L concentration range, oxidation peak current and concentration exist good linear relationship, and linear equation is Y=27.46X+49.30, and relation conefficient is R
2=0.9917, lowest detection is limited to 0.7 μ mol/L.
embodiment 5
(1) aniline monomer of 9.3598 g is dissolved in the aqueous solution of 250 ml and is configured to the aniline-water solution A that volumetric molar concentration is 0.4 mol/L;
(2) vitriol oil of 51.083 g is dissolved in to the aqueous sulfuric acid B that is configured to 1 mol/L in the water of 500 ml;
(3) get 20 ml solution A and 20 ml solution B and insert in electrochemical reaction cell and stir, form the sulphuric acid soln of the aniline of homogeneous transparent.
(4) in three-electrode system, at 20 DEG C of temperature, at the enterprising horizontal pulse electropolymerization of working electrode.Pulse signal is set to: apply pulsed voltage: 1.1 V(are with respect to saturated calomel electrode), controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:30, and pulse ETAD expected time of arrival and departure is 0.007s, and pulse number is 450.
(5) after polymerization, clean with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material, its molecular weight is that 16200, two phenyl ring and nitrogen-atoms key key angle are: 152 °.
Under three-electrode system, the above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to super capacitor performance test in the sulphuric acid soln of 0.5 mol/L, it reaches 923 F/g than electric capacity, discharges and recharges rear specific storage for 2000 times and remains on original 91%.
The above-mentioned single cisoid conformation polyaniline conductive polymer material preparing is carried out to sensor performance test.In three-electrode system, polyaniline film cathode prepared by single cisoid conformation polyaniline conductive polymer material of the present invention is as working electrode, taking the sulphuric acid soln of 0.1 mol/L as supporting electrolyte, the xitix that drips successively different concns carries out cyclic voltammetry scan.In the concentration X of xitix is 1 μ mol/L～0.1 mol/L concentration range, oxidation peak current and concentration exist good linear relationship, and linear equation is Y=32.42X+51.83, and relation conefficient is R
2=0.9961, lowest detection is limited to 2.4 μ mol/L.
Claims (7)
1. a single cisoid conformation polyaniline conductive polymer material, is characterized in that, the structural formula of described material is:
Wherein n=15-110, and in described material, phenyl ring is that the cis hand of spiral connects, and molecular weight is that 4500～30000, two phenyl ring and nitrogen-atoms angle are: 135 °～175 °.
2. single cisoid conformation polyaniline conductive polymer material as claimed in claim 1, is characterized in that, the ratio electric capacity of described single cisoid conformation polyaniline conductive polymer material is at 900～1200Fg
-1between.
3. single cisoid conformation polyaniline conductive polymer material as claimed in claim 1, is characterized in that, the good cycling stability of described single cisoid conformation polyaniline conductive polymer material, after 2000 times discharge and recharge specific storage remain on original 85% or more than.
4. single cisoid conformation polyaniline conductive polymer material as claimed in claim 3, is characterized in that, described single cisoid conformation polyaniline conductive polymer material specific storage after 2000 times discharge and recharge remain on original 95% or more than.
5. the preparation method of single cisoid conformation polyaniline conductive polymer material as described in as arbitrary in claim 1-3, comprises the following steps:
(1) aniline monomer and sulfuric acid are added in water, stir the sulphuric acid soln of the aniline that forms homogeneous transparent;
(2) in three-electrode system, the sulphuric acid soln of aniline is added in electrochemical reaction cell, at the enterprising horizontal pulse electropolymerization of working electrode, after polymerization, cleans with large water gaging, remove surface attachment reactant, obtain single cisoid conformation polyaniline conductive polymer material;
It is characterized in that: the pulse signal of described pulse is: pulsed voltage: 0.8～1.1 V, pulse ETAD expected time of arrival and departure is 0.001s～0.01s, and controlling subsequently electric current in time to chopping is zero, and pulse break make ratio is controlled at 1:100～1:10.
6. the preparation method of single cisoid conformation polyaniline conductive polymer material as claimed in claim 5, is characterized in that, the temperature of reaction of described electrochemical reaction is at 0-25 DEG C.
7. the preparation method of the single cisoid conformation polyaniline conductive polymer material as described in claim 5 or 6, is characterized in that, the temperature of reaction of described electrochemical reaction is 0 DEG C of left and right.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420329.4A CN102952268B (en) | 2012-10-29 | 2012-10-29 | Single cis-conformation polyaniline conducting polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420329.4A CN102952268B (en) | 2012-10-29 | 2012-10-29 | Single cis-conformation polyaniline conducting polymer material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952268A CN102952268A (en) | 2013-03-06 |
| CN102952268B true CN102952268B (en) | 2014-07-09 |
Family
ID=47761698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210420329.4A Expired - Fee Related CN102952268B (en) | 2012-10-29 | 2012-10-29 | Single cis-conformation polyaniline conducting polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102952268B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
| CN1958854A (en) * | 2006-10-11 | 2007-05-09 | 扬州大学 | Electrochemical method for synthesizing Nano fiber of polyaniline |
| CN100412110C (en) * | 2006-12-25 | 2008-08-20 | 李桂村 | Polyaniline nano fiber and its preparing process |
| CN101942090B (en) * | 2010-09-10 | 2012-01-25 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
-
2012
- 2012-10-29 CN CN201210420329.4A patent/CN102952268B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102952268A (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mujawar et al. | Electropolymerization of polyaniline on titanium oxide nanotubes for supercapacitor application | |
| Zhao et al. | Preparation of polyaniline nanowire arrayed electrodes for electrochemical supercapacitors | |
| CN104576080B (en) | An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode | |
| CN106328384B (en) | carbon quantum dot-polyaniline/carbon fibre integrated composite material and its preparation method and application | |
| Ran et al. | Preparation of hierarchical polyaniline nanotubes based on self‐assembly and its electrochemical capacitance | |
| CN102800432A (en) | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material | |
| CN103123870A (en) | Nanocomposite film electrode material for supercapacitor and producing method thereof | |
| CN106449146B (en) | Application of the graphene oxide-polyaniline composite material of three-dimensional structure in capacitor electrode material | |
| CN101012309A (en) | Method of preparing conductive macromolecule electrode material for super capacitor | |
| CN101942090A (en) | Preparation method of nano-fiber poly-aniline | |
| CN102760583A (en) | Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method | |
| CN103456508A (en) | Method for manufacturing graphene composite electrode | |
| Mondal et al. | Controlled growth of polypyrrole microtubes on disposable pencil graphite electrode and their supercapacitor behavior | |
| CN106024094B (en) | A kind of compliant conductive polyaniline nano fiber bumps electrode material and preparation method thereof | |
| CN103854875A (en) | Polyaniline/MnO2 compound modified three-dimensional graphene composite material, preparation method and application of composite material | |
| CN101710541B (en) | Preparation method of polyaniline nano-fiber electrode material for super capacitor | |
| US20090251849A1 (en) | Energy Storage Device Having Novel Energy Storage Means | |
| CN101492536B (en) | Nano-polyaniline material with morphology inheritance and electrochemical preparation method | |
| CN104828773A (en) | Nanowire in polypyrrole/silver@ silver sulfide core shell structure, use thereof and preparation method therefor | |
| CN103343394A (en) | Preparation method of polypyrrole nano fibers | |
| CN105551825A (en) | Electrochemical supercapacitor taking oxidation-reduction medium doped organic-phase gel as electrolyte | |
| CN102952268B (en) | Single cis-conformation polyaniline conducting polymer material and preparation method thereof | |
| CN103255433A (en) | Electrochemical synthesis method for rapid synthesis of conductive polyaniline under condition of heavy current | |
| KR20140095199A (en) | Method for preparing electroconductive polymer and thermoelectric device comprising electroconductive polymer film prepared using the same | |
| CN102157266B (en) | Flexible film super capacitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140709 Termination date: 20151029 |
|
| EXPY | Termination of patent right or utility model |