CN102505124B - Polypyrrole nanocolumn embedded nanoporous array material, preparation method thereof and energy storage application thereof - Google Patents
Polypyrrole nanocolumn embedded nanoporous array material, preparation method thereof and energy storage application thereof Download PDFInfo
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a polypyrrole nanocolumn embedded nanoporous array material. The pyrrole nanocolumn embedded nanoporous array material comprises a polypyrrole matrix, nanopores which are arranged on the polypyrrole matrix, are distributed in an array mode and respectively have two through ends, and polypyrrole nanocolumns embedded in the nanopores, and a gap is arranged between the cylindrical surface of each of the polypyrrole nanocolumns and the inner wall of each of the nanopores. The polypyrrole nanocolumn embedded nanoporous array material is obtained by covering a titanium dioxide nanotube composite array material with polypyrrole through carrying out an electropolymerization reaction regulated by a pulse voltammetry process, and completely removing a titanium dioxide ordered nanotube template by hydrofluoric acid through a chemical corrosion dissolution process, wherein the polypyrrole is obtained by compositing titanium dioxide nanotubes, polypyrrole nanofilms covered on exterior wall surfaces of the nanotubes and the polypyrrole nanocolumns embedded in cavities of the nanotubes and has a coaxial solid structure The polypyrrole nanocolumn embedded nanoporous array material of the invention can be used as a super capacitor electrode material for the electrochemical energy storage application.
Description
Technical field
The present invention relates to embedding nanometer pore array material of a kind of polypyrrole nano-pillar and preparation method thereof and the application of ultracapacitor electrochemical energy storage, belong to polymeric material field.
Background technology
Electric polypyrrole is a kind of typical conductive polymers, it has its good chemical stability, the rear high conductivity of doping, is easy to the advantages such as synthesis, pattern controllable, has good application prospect in fields such as stored energy, chemistry and biosensor, electromagnetic shielding and anti-corrosion of metal.In electrochemical energy storage Application Areas, the microstructure features of electric polypyrrole electrode materials is even more important, and high effective ratio area and the nano-array of proper alignment can increase ratio capacitance, the electrochemistry accumulate performance such as specific energy and specific power of electrode materials.Usually, α and the β position of pyrrole monomer has close response capacity, is very easily cross-linked to form particulate state polypyrrole in direct polymerization process, so far, has the polypyrrole nano particle of single nano structure, nanometer film and nano wire and has been reported.The polypyrrole nano structure electrode material aligned has good electroconductibility and physical strength, both improve the effective ratio area of polypyrrole, be conducive to again reactive ion diffusion and electric transmission, and the polypyrrole composite nanostructure electrode materials that design and synthesis aligns can improve its electrochemistry accumulate performance further, thus there is in supercapacitor applications good prospect.And the embedding nanometer pore array material of polypyrrole nano-pillar of the present invention is based on the proper alignment formed in polypyrrole nano-pillar embedding polypyrrole nanoporous, is uniformly distributed and has microstructure flexibility and the regulatable a kind of polypyrrole composite nanostructure array material of pattern, the application of electrochemistry high-efficiency energy-storage can be carried out as electrode material for super capacitor.
Summary of the invention
The invention provides embedding nanometer pore array material of a kind of polypyrrole nano-pillar and preparation method thereof, the invention provides the embedding nanometer pore array material of a kind of polypyrrole nano-pillar carries out electrochemical energy storage application as electrode material for super capacitor.
The present invention adopts following technical scheme to realize above-mentioned purpose:
The embedding nanometer pore array material of a kind of polypyrrole nano-pillar of the present invention, the described embedding nanometer pore array material of polypyrrole nano-pillar comprises: polypyrrole matrix, polypyrrole matrix is provided with in array distribution and the penetrating nanoporous in two ends, be embedded in polypyrrole nano-pillar at nanoporous, between polypyrrole nano-pillar cylinder and nanoporous inwall, be provided with gap.
The preparation method of the embedding nanometer pore array material of polypyrrole nano-pillar of the present invention, first, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as working electrode, platinized platinum is as negative electrode and as supporting electrode, with the aqueous solution of Neutral ammonium fluoride, phosphoric acid and ethylene glycol for reaction electrolyte solution, adopt constant voltage anodic oxidation reactions method, prepare that tube wall is spaced apart, in order and by the titania nanotube of arrayed, the titanium dioxide ordered nano-tube that the tube wall obtained is spaced apart is as template, then, in three-electrode electro Chemical reaction system, titanium dioxide ordered nano-tube template is as electrode base material and as working electrode, platinized platinum is as supporting electrode, saturated calomel electrode is as reference electrode, with the second cyanogen organic solution of pyrrole monomer and lithium perchlorate for reaction electrolyte solution, adopt the electric polymerization reaction method of regulation and control, polypyrrole deposits successively and is formed based on the polypyrrole nanometer film in tube wall face with based on intraluminal polypyrrole nano-pillar in titanium dioxide ordered nano-tube outside wall surface and tube chamber, obtain by titania nanotube, be coated on the polypyrrole nanometer film in nanotube outside wall surface and the polypyrrole cladding titanium dioxide nano pipe composite array material being embedded in the concentric shafts solid construction that the intraluminal polypyrrole nano-pillar of nanotube is composited.Finally, the polypyrrole cladding titanium dioxide nano pipe composite array material of above-mentioned preparation is precursor, adopts chemical corrosion solubilizing reaction method to remove titanium dioxide ordered nano-tube template completely, obtains the embedding nanometer pore array material of polypyrrole nano-pillar.
The embedding nanometer pore array material of polypyrrole nano-pillar of the present invention carries out the application of electrochemical energy storage as electrode material for super capacitor.
The embedding nanometer pore array material of polypyrrole nano-pillar of the present invention has the following advantages.
(1) polypyrrole nano-pillar embeds completely in polypyrrole nanoporous and forms orderly regular arrangement and equally distributed nano array structure, wherein said nanoporous has the penetrating feature in two ends, and nano-pillar has detached column structure and and keeps the feature of uniform gap between nanoporous wall.
(2) nanoporous can provide the nanochannel of complete permeability, keep uniform gap between nano-pillar cylinder and nanoporous inwall simultaneously, add effective ratio area on the one hand, optimize reactive ion directional migration path on the other hand, realization response ion short-range diffusion, is applied to electrode material for super capacitor and can improves electrochemistry accumulate performance.
(3) polypyrrole nanoporous and polypyrrole nano-pillar have the polypyrrole conducting film of regular ordered arrangement, electrochemical reaction generation electronics carries out axial orientation along polypyrrole conducting film under electric field action rule transmission, improve electronic conduction efficiency, be applied to electrode material for super capacitor and can improve electrochemistry accumulate performance.
(4) adopt the preparation method of electrochemistry and wet chemistry synthesis reaction, can carry out under the mild conditions of normal temperature and pressure, simple to operate, and also precursor material is easy to get, raw materials cost relative moderate.
Accompanying drawing explanation
Fig. 1 is the microstructure schematic diagram of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 2 is the scanning electron microscope front plan view of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 3 is the scanning electron microscope back side vertical view of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 4 is the scanning electron microscope side sectional view of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 5 is the Fourier transform infrared spectroscopy figure of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 6 is the continuous current cycle charge-discharge graphic representation of the embedding nanometer pore array material of polypyrrole nano-pillar.
Fig. 7 is the pulse potential regulation and control curve synoptic diagram of pulse voltammetry.
Fig. 8 is the scanning electron microscope front plan view that pulse voltammetry carries out electric polymerization reaction and prepares polypyrrole cladding titanium dioxide nano pipe composite array material.
Fig. 9 is the scanning electron microscope front plan view that regular circulation voltammetry is carried out electric polymerization reaction and prepared polypyrrole-titania nanotube composite array material.
Figure 10 is the scanning electron microscope front plan view that conventional potentiostatic method carries out electric polymerization reaction and prepares polypyrrole-titania nanotube composite array material.
Embodiment
Below by specific embodiment, further illustrate preparation method and the application of electrode of super capacitor electrochemical energy storage thereof of the embedding nanometer pore array material of polypyrrole nano-pillar.
Embodiment 1
The preparation method of polypyrrole ordered nano hole array material of the present invention comprises the following steps.
(1) the titanium dioxide ordered nano-tube template that tube wall is spaced apart is synthesized
First, pure for metal titanium sheet is cleaned 30min in ethanol, acetone, deionized water for ultrasonic successively, then, in 3.3mol/L hydrofluoric acid and 5.6mol/L aqueous nitric acid, chemical rightenning pre-treatment 8-15s is carried out, then, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as working electrode, platinized platinum is as negative electrode and as supporting electrode, with 0.2mol/L Neutral ammonium fluoride, the aqueous solution of 0.5mol/L phosphoric acid and 9.0mol/L ethylene glycol is reaction electrolyte solution, adopt constant voltage anodic oxidation reactions method, setting constant voltage is 30V, reaction times is 2h, temperature of reaction is 20-25 DEG C, prepare that tube wall is spaced apart, in order and by the titania nanotube of arrayed, the titanium dioxide ordered nano-tube that the tube wall obtained is spaced apart is as template, described template has the constitutional features having uniform gap between nanotube tube wall, finally, titanium dioxide ordered nano-tube template deionized water fully rinses, and naturally dry, and carry out the thermal treatment of 450 DEG C of roasting 2h, template is converted into Anatase crystal by amorphous non-crystalline state.
(2) the embedding nanometer pore array material of polypyrrole nano-pillar is synthesized
First, the titanium dioxide ordered nano-tube template of above-mentioned preparation is immersed sonic oscillation process 30-60min in pyrrole monomer; Then, in three-electrode electro Chemical reaction system, the electric polymerization reaction method of regulation and control adopts pulse voltammetry, titanium dioxide ordered nano-tube template is working electrode, platinized platinum is supporting electrode, saturated calomel electrode is reference electrode, with the second cyanogen solution of 0.15mol/L pyrroles and 0.10mol/L lithium perchlorate for reaction electrolyte solution, pulse voltammetry setting take-off potential is on the working electrode (s 0.7V, termination current potential is 1.1V, and current potential increment is 0.001V/s, and sampling time width is 0.02s, pulse width is 0.06s, and the recurrence interval is 4s.Pulse voltammetry is adopted to carry out the electric polymerization reaction regulated and controled, polypyrrole deposits successively and is formed based on the polypyrrole nanometer film in tube wall face with based on intraluminal polypyrrole nano-pillar in titanium dioxide ordered nano-tube outside wall surface and tube chamber, obtains by titania nanotube, is coated on the polypyrrole nanometer film in nanotube outside wall surface and is embedded in the polypyrrole cladding titanium dioxide nano pipe composite array material of the concentric shafts solid construction that the intraluminal polypyrrole nano-pillar of nanotube is composited.Finally, adopt chemical corrosion solubilizing reaction method, titanium dioxide ordered nano-tube template removed completely by polypyrrole cladding titanium dioxide nano pipe composite array material in hydrofluoric acid aqueous solution, obtains the described embedding nanometer pore array material of polypyrrole nano-pillar.Hydrofluoric acid volumetric molar concentration is 2.0mol/L, titanium dioxide corrosion dissolution reaction 30min.
Embodiment 2
The microstructure appearance analysis of the embedding nanometer pore array material of polypyrrole nano-pillar of the present invention and chemical structure analysis.
(1) the microstructure appearance analysis of the scanning electron microscope of the embedding nanometer pore array material of polypyrrole nano-pillar
The scanning electron microscope front and back vertical view display of the embedding nanometer pore array material of polypyrrole nano-pillar: polypyrrole nanotube embeds completely in polypyrrole nanoporous and forms orderly regular arrangement and equally distributed nano array structure, wherein said nanoporous has the penetrating feature in two ends, nano-pillar there is detached column structure and and keep the feature of uniform gap between nanoporous wall, nanoporous diameter range is 115-225nm, nanoporous length range is 700-1300nm, clearance distance scope between polypyrrole nano-pillar cylinder and nanoporous inwall is 15-45nm, , refer to Figure of description 2 and 3.Figure of description 4 is side scanning electron microscope (SEM) photographs of the embedding nanometer pore array material of polypyrrole nano-pillar, in figure, I is the side partly cut-away region of the embedding nanometer pore array material of polypyrrole nano-pillar, a polypyrrole nano-pillar is included in each polypyrrole nanoporous, and nano-pillar and nanoporous wall keep uniform gap, as can be seen here, the embedding nanometer pore array material of polypyrrole nano-pillar includes the nanoporous of two ends permeability and the nano-pillar of detached column structure simultaneously, and nano-pillar embeds nanoporous and forms concentric shafts solid construction.
(2) chemical structure analysis of the infrared spectra of the embedding nanometer pore array material of polypyrrole nano-pillar
The Fourier transform infrared spectroscopy figure of the embedding nanometer pore array material of polypyrrole nano-pillar shows: wave number 1564cm
-1the crest at place is the stretching vibration absorption peak of C=C double bond, wave number 1211cm
-1the crest at place is the stretching vibration absorption peak of C-N key, wave number 1042cm
-1the crest at place is the in-plane bending vibration absorption peak of N-H key, wave number 929cm
-1and 790cm
-1the crest at place is the out-of-plane deformation vibration absorption peak of c h bond.Results of IR is all shown as the charateristic avsorption band of polypyrrole, there is not the charateristic avsorption band of titanium dioxide, synthetic sample is the embedding nanometer pore array material of polypyrrole nano-pillar removing titanium dioxide ordered nano-tube template completely, refers to Figure of description 5.
Embodiment 3
The embedding nanometer pore array material of polypyrrole nano-pillar of the present invention is as the application of the electrochemical energy storage of electrode material for super capacitor.
It is as follows that the embedding nanometer pore array material of polypyrrole nano-pillar carries out the performance test of electrochemistry accumulate as electrode material for super capacitor: in three electrode charge and discharge test systems, with the 1.0M lithium perchlorate aqueous solution for Working electrolyte, the embedding nanometer pore array material of polypyrrole nano-pillar is working electrode, platinized platinum is supporting electrode, saturated calomel electrode is reference electrode, adopt electrochemical workstation (IM6e, ZAHNER Elektrik, Germany) carry out continuous current cycle charge discharge electrical testing, the constant current density of setting cycle charge discharge electrical testing is 0.25mA/cm
2, calculate electrochemical capacitor according to continuous current cycle charge-discharge test data of experiment, the area ratio electrical capacity of the embedding nanometer pore array material of polypyrrole nano-pillar is 18.33mF cm
-2, refer to Figure of description 6.
Embodiment 4
The preparation method of the embedding nanometer pore array material of polypyrrole nano-pillar of the present invention, the electric polymerization reaction method adopting pulse voltammetry to carry out regulating and controlling prepares polypyrrole cladding titanium dioxide nano pipe composite array material.
For the titanium dioxide ordered nano-tube template that tube wall is spaced apart, on the one hand, the specific conductivity of the tube wall gap area between adjacent nanotubes is higher than the specific conductivity of the tube chamber inner compartment of nanotube, on the other hand, pyrroles's electric polymerization reaction has the electrochemical reaction dynamic characteristic that reactive ion diffusive migration controls, therefore, adopt pulse voltammetry to be more conducive to pyrrole monomer and carry out directed diffusive migration and the electric polymerization reaction of location.Pulse voltammetry setup control parameter of the present invention is as follows: with the second cyanogen organic solution of pyrrole monomer and lithium perchlorate in reaction electrolyte solution, the volumetric molar concentration of pyrrole monomer is 0.15mol/L, the volumetric molar concentration scope of lithium perchlorate is 0.10mol/L, the take-off potential of working electrode is 0.7V, termination current potential is 1.1V, current potential increment is 0.001V/s, pulse width is 0.06s, recurrence interval scope is 4s, about the pulse potential regulation and control curve synoptic diagram of pulse voltammetry, with reference to Figure of description 7.Experimental result shows, pulse voltammetry is adopted to carry out the electric polymerization reaction regulated and controled, polypyrrole deposits successively and is formed based on the polypyrrole nanometer film in tube wall face with based on intraluminal polypyrrole nano-pillar in titanium dioxide ordered nano-tube outside wall surface and tube chamber, obtain by titania nanotube, be coated on the polypyrrole nanometer film in nanotube outside wall surface and be embedded in the polypyrrole cladding titanium dioxide nano pipe composite array material of the concentric shafts solid construction that the intraluminal polypyrrole nano-pillar of nanotube is composited, with reference to Figure of description 8.Therefore, pulse voltammetry of the present invention is different from regular circulation voltammetry, conventional potentiostatic method and conventional galvanostatic method, adopt pulse voltammetry to regulate and control electric polymerization reaction, prepare the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts solid construction.
Embodiment 5
The embedding nanometer pore array material of a kind of polypyrrole nano-pillar, microstructure schematic diagram is with reference to Figure of description 1, in figure, 1 represents polypyrrole matrix, in figure, 2 represent nanoporous, in figure, 2 represent polypyrrole nano-pillar, the described embedding nanometer pore array material of polypyrrole nano-pillar comprises: polypyrrole matrix 1, polypyrrole matrix 1 is provided with in array distribution and the penetrating nanoporous 2 in two ends, polypyrrole nano-pillar 3 is embedded at nanoporous 2, gap is provided with between polypyrrole nano-pillar 3 cylinder and nanoporous 2 inwall, the diameter range of nanoporous 2 is 115-225nm, the length range of nanoporous 2 is 700-1300nm, gap between polypyrrole nano-pillar cylinder and nanoporous inwall is 15-45nm.
Reference examples 1
This reference examples adopts regular circulation voltammetry to carry out electric polymerization reaction method to prepare polypyrrole-titania nanotube composite array material.Described regular circulation voltammetry setup control parameter is as follows: with the second cyanogen solution of volumetric molar concentration 0.15mol/L pyrrole monomer and volumetric molar concentration 0.10mol/L lithium perchlorate for reaction electrolyte solution, titanium dioxide ordered nano-tube template is 0.5-1.1V as the electric potential scanning scope of working electrode, potential scan rate is 5mV/s, and scan round number of times is 10 times.The microstructure appearance characterization result display of polypyrrole-titanium dioxide composite nano tube, pyrrole monomer carries out electric polymerization reaction in a part of region on the titania nanotube mouth of pipe or surface and forms the polypyrrole nanometer film tectum of local, shown in II in Figure of description 9, polypyrrole nanometer film tectum is not formed in another part region on the titania nanotube mouth of pipe or surface, shown in III in Figure of description 9, in the tube wall face and tube chamber of titania nanotube, all do not form polypyrrole nanometer film.As can be seen here, regular circulation voltammetry is adopted to carry out electric polymerization reaction, in the tube wall face that polypyrrole cannot regulate and control to be deposited on titania nanotube or tube chamber, the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts solid construction cannot be formed, thus cannot prepare the embedding nanometer pore array material of polypyrrole nano-pillar.
Reference examples 2
This reference examples adopts conventional potentiostatic method to carry out electric polymerization reaction method to prepare polypyrrole-titania nanotube composite array material.
Adopt conventional potentiostatic method to carry out electric polymerization reaction and prepare polypyrrole-titanium dioxide composite nano tube, described conventional potentiostatic method setup control parameter is as follows: the second cyanogen solution of volumetric molar concentration 0.15mol/L pyrrole monomer and volumetric molar concentration 0.10mol/L lithium perchlorate is reaction electrolyte solution, titanium dioxide ordered nano-tube template is 0.8V as the constant potential of working electrode, and the electric polymerization reaction time is 1200s.The microstructure appearance characterization result display of polypyrrole-titanium dioxide composite nano tube, pyrrole monomer carries out electric polymerization reaction at the surf zone of titania nanotube and forms polypyrrole nano particle, all polypyrrole nanometer film is not formed, with reference to Figure of description 10 in the tube wall face of nanotube and tube chamber.As can be seen here, conventional potentiostatic method is adopted to carry out electric polymerization reaction, in the tube wall face that polypyrrole cannot regulate and control to be deposited on titania nanotube or tube chamber, the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts solid construction cannot be formed, thus cannot prepare the embedding nanometer pore array material of polypyrrole nano-pillar.
Embodiment 5
The embedding nanometer pore array material of a kind of polypyrrole nano-pillar, the described embedding nanometer pore array material of polypyrrole nano-pillar comprises: polypyrrole matrix 1, polypyrrole matrix 1 is provided with in array distribution and the penetrating nanoporous 2 in two ends, polypyrrole nano-pillar 3 is embedded at nanoporous 2, gap is provided with between polypyrrole nano-pillar 3 cylinder and nanoporous 2 inwall, in the present embodiment, the diameter range of described nanoporous 2 is 115-225nm, the length range of nanoporous 2 is 700-1300nm, and the distance range in gap is 15-45nm.
Claims (3)
1. the preparation method of the embedding nanometer pore array material of polypyrrole nano-pillar, it is characterized in that: first, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as working electrode, platinized platinum is as negative electrode and as supporting electrode, with the aqueous solution of Neutral ammonium fluoride, phosphoric acid and ethylene glycol for reaction electrolyte solution, adopt constant voltage anodic oxidation reactions method, prepare that tube wall is spaced apart, in order and by the titania nanotube of arrayed, the titanium dioxide ordered nano-tube that the tube wall obtained is spaced apart is as template, then, in three-electrode electro Chemical reaction system, titanium dioxide ordered nano-tube template is as electrode base material and as working electrode, platinized platinum is as supporting electrode, saturated calomel electrode is as reference electrode, with the second cyanogen organic solution of pyrrole monomer and lithium perchlorate for reaction electrolyte solution, adopt the electric polymerization reaction method of regulation and control, polypyrrole deposits successively and is formed based on the polypyrrole nanometer film in tube wall face with based on intraluminal polypyrrole nano-pillar in titanium dioxide ordered nano-tube outside wall surface and tube chamber, obtain by titania nanotube, be coated on the polypyrrole nanometer film in nanotube outside wall surface and the polypyrrole cladding titanium dioxide nano pipe composite array material being embedded in the concentric shafts solid construction that the intraluminal polypyrrole nano-pillar of nanotube is composited, finally, the polypyrrole cladding titanium dioxide nano pipe composite array material of described preparation is precursor, chemical corrosion solubilizing reaction method is adopted to remove titanium dioxide ordered nano-tube template completely, obtain the embedding nanometer pore array material of polypyrrole nano-pillar,
The electric polymerization reaction method of regulation and control adopts pulse voltammetry to prepare polypyrrole cladding titanium dioxide nano pipe composite array material, described pulse voltammetry setting take-off potential is on the working electrode (s 0.7 V, stopping current potential is 1.1 V, and current potential increment is 0.001 V s
-1, sampling time width is 0.02 s, and pulse width is 0.06 s, and recurrence interval scope is 3-6 s; The electrolyte solution of the electric polymerization reaction of described regulation and control is volumetric molar concentrations is 0.15 mol/L pyrrole monomer, volumetric molar concentration scope is 0.08-0.12 mol/L lithium perchlorate and the second cyanogen organic solvent as reaction medium.
2. preparation method according to claim 1, it is characterized in that: described constant voltage anodic oxidation reactions method is: setting constant voltage is 30 V, reaction times is 2 h, temperature of reaction is 20-25 DEG C, with the aqueous solution of Neutral ammonium fluoride, phosphoric acid and ethylene glycol in reaction electrolyte solution, Neutral ammonium fluoride volumetric molar concentration is 0.2 mol/L, and phosphoric acid volumetric molar concentration is 0.5 mol/L, and ethylene glycol volumetric molar concentration is 9.0 mol/L.
3. the preparation method of the embedding nanometer pore array material of a kind of polypyrrole nano-pillar according to claim 1, it is characterized in that: described chemical corrosion solubilizing reaction method adopts the method for hydrofluoric acid corrosion titanium dioxide, the described embedding nanometer pore array material of polypyrrole nano-pillar is obtained after titanium dioxide ordered nano-tube template removed completely by polypyrrole cladding titanium dioxide nano pipe composite array material in hydrofluoric acid aqueous solution, the titanium dioxide corrosion dissolution reaction times is 20-40 min, and hydrofluoric acid volumetric molar concentration scope is 1.5-2.5 mol/L.
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| CN1465748A (en) * | 2002-06-26 | 2004-01-07 | 天津大学 | Method for directly forming polypyrrole nano line on electrode surface |
| CN101037787A (en) * | 2007-01-25 | 2007-09-19 | 西安交通大学 | Preparation technique of high-density polypyrrole film anticorrosive coating |
| CN101955665A (en) * | 2010-08-18 | 2011-01-26 | 重庆大学 | Method for preparing composite material of polypyrrole granules and titanium dioxide nanotube array |
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| JPS63274790A (en) * | 1987-04-30 | 1988-11-11 | Mitsubishi Rayon Co Ltd | Thin polymer film having superior surface smoothness and production thereof |
| CN1465748A (en) * | 2002-06-26 | 2004-01-07 | 天津大学 | Method for directly forming polypyrrole nano line on electrode surface |
| CN101037787A (en) * | 2007-01-25 | 2007-09-19 | 西安交通大学 | Preparation technique of high-density polypyrrole film anticorrosive coating |
| CN101955665A (en) * | 2010-08-18 | 2011-01-26 | 重庆大学 | Method for preparing composite material of polypyrrole granules and titanium dioxide nanotube array |
| CN101979438A (en) * | 2010-11-25 | 2011-02-23 | 武汉大学 | Preparation method of conductive polypyrrole |
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