CN102522210B - Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof - Google Patents
Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof Download PDFInfo
- Publication number
- CN102522210B CN102522210B CN201110362862.5A CN201110362862A CN102522210B CN 102522210 B CN102522210 B CN 102522210B CN 201110362862 A CN201110362862 A CN 201110362862A CN 102522210 B CN102522210 B CN 102522210B
- Authority
- CN
- China
- Prior art keywords
- polypyrrole
- nano
- titanium dioxide
- nanotube
- array material
- 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
Classifications
-
- 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
Abstract
The invention discloses a polypyrrole nano-tube embedded nano-pore array material. The polypyrrole nano-tube embedded nano-pore array material comprises a polypyrrole basal body, wherein the polypyrrole basal body is provided with nano-pores which are distributed in arrays and each of which has two through ends; polypyrrole nano-tubes are embedded in the nano-pores; and a gap is arranged between each of the outer walls of the polypyrrole nano-tubes and each of the inner walls of the nano-pores. A polypyrrole coated titanium dioxide nano-tube compound array material, which is of a concentric-shaft hollow structure and formed by compounding titanium dioxide nano-tubes, polypyrrole nano-films coated on the outer wall faces of the nano-tubes and polypyrrole nano-films coated on the inner wall faces of the nano-tubes, is obtained by using an electrical polymerization reaction method regulated and controlled by using pulse voltammetry, and a titanium dioxide sequential nano-tube template is completely removed by using hydrofluoric acid according to a chemical corrosion dissolution method to obtain the polypyrrole nano-tube embedded nano-pore array material. The polypyrrole nano-tube embedded nano-pore array material is subjected to electro-chemical energy storage application as a super-capacitor electrode material.
Description
Technical field
The present invention relates to a kind of polypyrrole nanotube embedding nanometer pore array material and preparation method thereof and the application of ultracapacitor electrochemical energy storage, belong to polymeric material field.
Background technology
Conducting polymer has non-localized pi-electron conjugated system, after ion doping, possesses certain conductivity, it had both had metal and semi-conductive conductive characteristic, lightweight, flexibility and machinable characteristic of polymer are retained again, therefore, conducting polymer all has broad application prospects in fields such as the energy, information, photoelectron, chemistry and biology sensor, electromagnetic shielding and anti-corrosion of metal, and common conducting polymer has polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene and derivative thereof etc.
Electric polypyrrole is a kind of typical conducting polymer, and it has high conductivity after its good chemical stability, doping, it is synthetic to be easy to and pattern such as can regulate and control at the advantage.In electrochemical energy storage application, the microstructure features of electric polypyrrole electrode material is even more important, and high effective ratio area and the nano-array of proper alignment can increase the electrochemistry accumulate performances such as ratio electric capacity, specific energy and the specific power of electrode material.So far, polypyrrole nano particle, nanometer film and the nano wire with single nano structure have been reported, the polypyrrole nano structure electrode material aligning has good conductivity and mechanical strength, both improved the effective ratio area of polypyrrole, be conducive to again reactive ion diffusion and electric transmission, and the synthetic polypyrrole composite nanostructure electrode material aligning of design can further improve its electrochemistry accumulate performance, thereby in supercapacitor applications, there is good prospect.Polypyrrole nanotube embedding nanometer pore array material of the present invention is to embed in polypyrrole nano-pore and the proper alignment forming, be uniformly distributed and have micro-structural flexibility and the regulatable a kind of polypyrrole composite nanostructure array material of pattern based on polypyrrole nanotube, can be used as electrode material for super capacitor and carries out the application of electrochemistry high-efficiency energy-storage.
Summary of the invention
The invention provides a kind of polypyrrole nanotube embedding nanometer pore array material and preparation method thereof, the invention provides a kind of polypyrrole nanotube embedding nanometer pore array material and carry out the application of electrochemical energy storage as electrode material for super capacitor.
The present invention adopts following technical scheme to realize above-mentioned purpose:
A kind of polypyrrole nanotube embedding nanometer pore array material of the present invention, described polypyrrole nanotube embedding nanometer pore array material comprises: polypyrrole matrix, on polypyrrole matrix, be provided with and be the penetrating nano-pore of array distribution and two ends, be embedded in polypyrrole nanotube at nano-pore, between polypyrrole nanotube outer wall and nano-pore inwall, be provided with gap.
The preparation method of polypyrrole nanotube embedding nanometer pore array material of the present invention, first, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as auxiliary electrode, taking the aqueous solution of ammonium fluoride, phosphoric acid and ethylene glycol as 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 obtaining is spaced apart is as template, then, in three-electrode electro Chemical reaction system, template is as electrode matrix material and as work electrode, platinized platinum is as auxiliary electrode, saturated calomel electrode is as reference electrode, taking the second cyanogen organic solution of pyrrole monomer and lithium perchlorate as reaction electrolyte solution, adopt the electric polymerization reaction method of regulation and control, polypyrrole is deposited successively on titanium dioxide ordered nano-tube outside wall surface and internal face and forms complete packet to be overlying on the polypyrrole nanometer film in titania nanotube outside wall surface, obtain by titania nanotube, be coated on polypyrrole nanometer film in nanotube outside wall surface and be coated on the polypyrrole cladding titanium dioxide nano pipe composite array material of the concentric shafts hollow structure that the polypyrrole nanometer film on nanotube internal face is composited, finally, taking polypyrrole cladding titanium dioxide nano pipe composite array material as precursor, adopt chemical corrosion solubilizing reaction method to remove titanium dioxide ordered nano-tube template completely, obtain polypyrrole nanotube embedding nanometer pore array material.
Polypyrrole nanotube embedding nanometer pore array material of the present invention carries out the application of electrochemical energy storage as electrode material for super capacitor.
Polypyrrole nanotube embedding nanometer pore array material of the present invention has the following advantages.
(1) polypyrrole nanotube embeds in polypyrrole nano-pore, form orderly regular arrangement and equally distributed nano array structure completely, wherein said nano-pore and nanotube all have the penetrating feature in two ends, nanotube have individual tubes wall construction and and nano-pore wall between keep the feature of uniform gap.
(2) polypyrrole nano-pore and polypyrrole nanotube can provide the nanochannel of complete permeability, and keep uniform gap between nanotube outer wall and nano-pore inwall, increase on the one hand effective ratio area, optimize on the other hand reactive ion directional migration path, realization response ion short-range diffusion, is applied to electrode material for super capacitor and can improves electrochemistry accumulate performance.
(3) polypyrrole nano-pore and polypyrrole nanotube have the polypyrrole conducting film of regular ordered arrangement, electrochemical reaction produces electronics and carry out axial oriented and ordered transmission along polypyrrole conducting film under electric field action, improve electrical conductivity efficiency, be applied to electrode material for super capacitor and can improve electrochemistry accumulate performance.
(4) adopt the preparation method of electrochemistry and wet-chemical synthetic reaction, can under the temperate condition of normal temperature and pressure, carry out, simple to operate, and also precursor material is easy to get, and cost of material is relatively cheap.
Brief description of the drawings
Fig. 1 is the micro-structural schematic diagram of polypyrrole nanotube embedding nanometer pore array material.
Fig. 2 is the ESEM front plan view of polypyrrole nanotube embedding nanometer pore array material.
Fig. 3 is the ESEM back side vertical view of polypyrrole nanotube embedding nanometer pore array material.
Fig. 4 is the ESEM side sectional view of polypyrrole nanotube embedding nanometer pore array material.
Fig. 5 is the Fourier transform infrared spectroscopy figure of polypyrrole nanotube embedding nanometer pore array material.
Fig. 6 is the constant current cycle charge-discharge curve chart of polypyrrole nanotube embedding nanometer pore array material.
Fig. 7 is the pulse potential regulation and control curve synoptic diagram of pulse voltammetry.
Fig. 8 is that pulse voltammetry carries out the ESEM front plan view that electric polymerization reaction is prepared polypyrrole cladding titanium dioxide nano pipe composite array material.
Fig. 9 is that regular circulation voltammetry is carried out the ESEM front plan view that electric polymerization reaction is prepared polypyrrole-titanium dioxide composite nano-tube material.
Figure 10 is that conventional potentiostatic method carries out the ESEM front plan view that electric polymerization reaction is prepared polypyrrole-titanium dioxide composite nano-tube material.
Embodiment
Below by specific embodiment, further illustrate preparation method and the application of electrode of super capacitor electrochemical energy storage thereof of polypyrrole nanotube embedding nanometer pore array material.
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 synthetic tube wall is spaced apart
First, pure metal titanium sheet is cleaned to 30min in ethanol, acetone, deionized water for ultrasonic successively, then, in 3.3mol/L hydrofluoric acid and 5.6mol/L aqueous solution of nitric acid, carry out chemical polishing preliminary treatment 8-15s, then, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as auxiliary electrode, with 0.2mol/L ammonium fluoride, the aqueous solution of 0.5mol/L phosphoric acid and 9.0mol/L ethylene glycol is reaction electrolyte solution, setting constant voltage is 30V, reaction time is 2h, reaction temperature is 20-25 DEG C, 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 obtaining is spaced apart is as template, described template has the architectural feature that has uniform gap between nanotube tube wall, finally, titanium dioxide ordered nano-tube template is fully rinsed with deionized water, naturally dries, and carries out the heat treatment of 450 DEG C of roasting 2h, and template is converted into Anatase crystal by amorphous amorphous state.
(2) synthetic polypyrrole nanotube embedding nanometer pore array material
First, the titanium dioxide ordered nano-tube template of above-mentioned preparation is immersed to sonic oscillation in pyrrole monomer and process 30-60min; 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 work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, taking the second cyanogen solution of 0.18mol/L lithium perchlorate and 0.15mol/L pyrrole monomer as reaction electrolyte solution, the take-off potential that pulse voltammetry is set on work electrode is 0.7V, termination current potential is 1.1V, and current potential increment is 0.001V/s, and sampling time width is 0.02s, pulse duration is 0.06s, and the pulse period is 4s.The electric polymerization reaction that adopts pulse voltammetry to regulate and control, polypyrrole is deposited successively on titanium dioxide ordered nano-tube outside wall surface and internal face and form complete packet to be overlying on the polypyrrole nanometer film on nanotube tube wall face, obtain by titania nanotube, be coated on the polypyrrole nanometer film in nanotube outside wall surface and be coated on the polypyrrole nanotube embedding nanometer pore array material of the concentric shafts hollow structure that the polypyrrole nanometer film on nanotube internal face is composited.Finally, adopt chemical corrosion solubilizing reaction method, polypyrrole cladding titanium dioxide nano pipe composite array material is removed titanium dioxide ordered nano-tube template completely in hydrofluoric acid aqueous solution, obtains described polypyrrole nanotube embedding nanometer pore array material.Hydrofluoric acid molar concentration is 2.0mol/L, titanium dioxide corrosion dissolution reaction 30min.
Embodiment 2
Microstructure appearance analysis and the chemical structure analysis of polypyrrole nanotube embedding nanometer pore array material of the present invention.
(1) the microstructure appearance analysis of the ESEM of polypyrrole nanotube embedding nanometer pore array material
The ESEM front and back vertical view of polypyrrole nanotube embedding nanometer pore array material shows: polypyrrole nanotube embeds in polypyrrole nano-pore, form orderly regular arrangement and equally distributed nano array structure completely, wherein said nano-pore and nanotube all have the penetrating feature in two ends, nanotube have individual tubes wall construction and and nano-pore wall between keep the feature of uniform gap, nano-pore diameter range is 115-225nm, nano-pore length range is 700-1300nm, clearance distance scope between polypyrrole nanotube outer wall and nano-pore inwall is 15-45nm, refer to Figure of description 2 and 3.Figure of description 4 is ESEM profiles of polypyrrole nanotube embedding nanometer pore array material, in figure, I is the side partly cut-away region of polypyrrole nanotube embedding nanometer pore array material, in each polypyrrole nano-pore, include a polypyrrole nanotube, between nanotube outside wall surface and nano-pore internal face, keep uniform gap, and the complete conducting of nanotube zone line, as can be seen here, polypyrrole nanotube embedding nanometer pore array material has the nanochannel feature of complete conduction, and nanotube embeds nano-pore and forms concentric shafts hollow structure.
(2) chemical structure analysis of the infrared spectrum of polypyrrole nanotube embedding nanometer pore array material
The Fourier transform infrared spectroscopy figure of polypyrrole nanotube embedding nanometer pore array material shows: wave number 1564cm
-1the crest at place is the stretching vibration peak of the two keys of C=C, wave number 1216cm
-1the crest at place is the stretching vibration peak of C-N key, wave number 1041cm
-1the crest at place is the in-plane bending vibration peak of N-H key, wave number 930cm
-1and 786cm
-1the crest at place is the out-of-plane bending vibration peak of c h bond.Results of IR is all shown as the eigen vibration peak of polypyrrole, there is not the eigen vibration peak of titanium dioxide, synthetic sample is the polypyrrole nanotube embedding nanometer pore array material that removes titanium dioxide ordered nano-tube template completely, refers to Figure of description 5.
Embodiment 3
Polypyrrole nanotube embedding nanometer pore array material of the present invention is as the application of the electrochemical energy storage of electrode material for super capacitor.
It is as follows that polypyrrole nanotube embedding nanometer pore array material carries out the performance test of electrochemistry accumulate as electrode material for super capacitor: in three electrode charge and discharge test systems, taking the 1.0M lithium perchlorate aqueous solution as Working electrolyte, polypyrrole nanotube embedding nanometer pore array material is work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, adopt electrochemical workstation (IM6e, ZAHNER Elektrik, Germany) carry out constant 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 constant current cycle charge-discharge test data of experiment, the Area Ratio capacitance of polypyrrole nanotube embedding nanometer pore array material is 16.67mF/cm
2, refer to Figure of description 6.
Embodiment 4
The preparation method of polypyrrole nanotube embedding nanometer pore array material of the present invention, the electric polymerization reaction method that adopts pulse voltammetry to regulate and control is prepared polypyrrole cladding titanium dioxide nano pipe composite array material.
The titanium dioxide ordered nano-tube that tube wall is spaced apart is as template, on the one hand, the conductivity of the tube wall gap area between adjacent nanotube is higher than the conductivity of the tube chamber inner region of nanotube, on the other hand, pyrroles's electric polymerization reaction has the electrochemical reaction dynamic characteristic of reactive ion diffusive migration control, 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: taking the second cyanogen organic solution of pyrrole monomer and lithium perchlorate in reaction electrolyte solution, the molar concentration of pyrrole monomer is 0.15mol/L, the molar concentration scope of lithium perchlorate is 0.15mol/L, the take-off potential of work electrode is 0.7V, termination current potential is 1.1V, current potential increment is 0.001V/s, pulse duration is 0.06s, pulse period 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, the electric polymerization reaction that adopts pulse voltammetry to regulate and control, polypyrrole is deposited successively on titanium dioxide ordered nano-tube outside wall surface and internal face and forms complete packet to be overlying on the polypyrrole nanometer film on nanotube tube wall face, obtain by titania nanotube, be coated on the polypyrrole nanometer film in nanotube outside wall surface and be coated on the polypyrrole nanotube embedding nanometer pore array material of the concentric shafts hollow structure that the polypyrrole nanometer film on nanotube internal face 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 can regulate and control electric polymerization reaction, prepare the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts hollow structure.
Embodiment 5
A kind of polypyrrole nanotube embedding nanometer pore array material, micro-structural schematic diagram is with reference to Figure of description 1, in figure, 1 represents polypyrrole matrix, in figure, 2 represent nano-pore, in figure, 2 represent polypyrrole nanotube, described polypyrrole nanotube embedding nanometer pore array material comprises: polypyrrole matrix 1, on polypyrrole matrix 1, be provided with and be the penetrating nano-pore 2 of array distribution and two ends, be embedded in polypyrrole nanotube 3 at nano-pore 2, between polypyrrole nanotube 3 outer walls and nano-pore 2 inwalls, be provided with gap, the diameter range of nano-pore 2 is 115-225nm, the length range of nano-pore 2 is 700-1300nm, the distance range in gap is 15-45nm.
Reference examples 1
This reference examples is to adopt regular circulation voltammetry to carry out electric polymerization reaction method to prepare polypyrrole-titanium dioxide composite nano-tube material.
Adopt regular circulation voltammetry to carry out electric polymerization reaction and prepare polypyrrole-titanium dioxide composite nano tube, described regular circulation voltammetry setup parameter is as follows: taking the second cyanogen solution of molar concentration 0.15mol/L pyrrole monomer and molar concentration 0.10mol/L lithium perchlorate as reaction electrolyte solution, titanium dioxide ordered nano-tube template is 0.5-1.1V as the electric potential scanning scope of work electrode, electric potential scanning speed is 5mV/s, and scan round number of times is 10 times.The microstructure appearance characterization result of polypyrrole-titanium dioxide composite nano tube shows, pyrrole monomer carries out electric polymerization reaction and forms local polypyrrole nanometer film cover layer in a part of region on the titania nanotube mouth of pipe or surface, with reference in Figure of description 9 shown in II, another part region on the titania nanotube mouth of pipe or surface does not form polypyrrole nanometer film cover layer, with reference in Figure of description 9 shown in III, in the tube wall face of titania nanotube and tube chamber, all do not form polypyrrole nanometer film.As can be seen here, adopt regular circulation voltammetry to carry out electric polymerization reaction, polypyrrole cannot regulate and control to be deposited in the tube wall face or tube chamber of titania nanotube, the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts hollow structure cannot be formed, thereby polypyrrole nanotube embedding nanometer pore array material cannot be prepared.
Reference examples 2
This reference examples is to adopt conventional potentiostatic method to carry out electric polymerization reaction method to prepare polypyrrole-titanium dioxide composite nano-tube material.
Adopt conventional potentiostatic method to carry out electric polymerization reaction and prepare polypyrrole-titanium dioxide composite nano tube, described conventional potentiostatic method setup parameter is as follows: the second cyanogen solution of molar concentration 0.15mol/L pyrrole monomer and 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 work electrode, and the electric polymerization reaction time is 1200s.The microstructure appearance characterization result of polypyrrole-titanium dioxide composite nano tube shows, pyrrole monomer carries out electric polymerization reaction and forms polypyrrole nano particle at the surf zone of titania nanotube, in the tube wall face of nanotube and tube chamber, all do not form polypyrrole nanometer film, with reference to Figure of description 10.As can be seen here, adopt conventional potentiostatic method to carry out electric polymerization reaction, polypyrrole cannot regulate and control to be deposited in the tube wall face or tube chamber of titania nanotube, the polypyrrole cladding titanium dioxide nano pipe composite array material of concentric shafts hollow structure cannot be formed, thereby polypyrrole nanotube embedding nanometer pore array material cannot be prepared.
Claims (3)
1. the preparation method of a polypyrrole nanotube embedding nanometer pore array material, it is characterized in that: first, in two electrode electro Chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as auxiliary electrode, taking the aqueous solution of ammonium fluoride, phosphoric acid and ethylene glycol as 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 obtaining is spaced apart is as template, then, in three-electrode electro Chemical reaction system, titanium dioxide ordered nano-tube template is as electrode matrix material and as work electrode, platinized platinum is as auxiliary electrode, saturated calomel electrode is as reference electrode, taking the second cyanogen organic solution of pyrrole monomer and lithium perchlorate as reaction electrolyte solution, adopt the electric polymerization reaction method of regulation and control, polypyrrole is deposited successively on titanium dioxide ordered nano-tube outside wall surface and internal face and forms complete packet to be overlying on the polypyrrole nanometer film on nanotube tube wall face, obtain by titania nanotube, be coated on polypyrrole nanometer film in nanotube outside wall surface and be coated on the polypyrrole cladding titanium dioxide nano pipe composite array material of the concentric shafts hollow structure that the polypyrrole nanometer film on nanotube internal face is composited, finally, taking polypyrrole cladding titanium dioxide nano pipe composite array material as precursor, adopt chemical corrosion solubilizing reaction method to remove titanium dioxide ordered nano-tube template completely, obtain polypyrrole nanotube embedding nanometer pore array material, the electric polymerization reaction method of regulation and control adopts pulse voltammetry, described pulse voltammetry is: the take-off potential being set on work electrode is 0.7V, termination current potential is 1.1V, current potential increment is 0.001V/s, sampling time width is 0.02s, pulse duration is 0.06s, pulse period scope is 3-6s, taking the second cyanogen organic solution of pyrrole monomer and lithium perchlorate in reaction electrolyte solution, the molar concentration of pyrrole monomer is 0.15mol/L, the molar concentration scope of lithium perchlorate is 0.15-0.20mol/L.
2. preparation method according to claim 1, it is characterized in that: described constant voltage anodic oxidation reactions method is: setting constant voltage is 30V, reaction time is 2h, reaction temperature is 20-25 DEG C, taking the aqueous solution of ammonium fluoride, phosphoric acid and ethylene glycol in reaction electrolyte solution, ammonium fluoride molar concentration is 0.2mol/L, and phosphoric acid molar concentration is 0.5mol/L, and ethylene glycol molar concentration is 9.0mol/L.
3. preparation method 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 method of described hydrofluoric acid corrosion titanium dioxide is: polypyrrole cladding titanium dioxide nano pipe composite array material is immersed in hydrofluoric acid aqueous solution completely, titanium dioxide generation chemical corrosion solubilizing reaction, after removing template completely, obtain described polypyrrole nanotube embedding nanometer pore array material, titanium dioxide corrosion dissolution reaction time range is 20-40min, hydrofluoric acid molar concentration scope is 1.5-2.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110362862.5A CN102522210B (en) | 2011-11-16 | 2011-11-16 | Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110362862.5A CN102522210B (en) | 2011-11-16 | 2011-11-16 | Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102522210A CN102522210A (en) | 2012-06-27 |
| CN102522210B true CN102522210B (en) | 2014-11-19 |
Family
ID=46293098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110362862.5A Expired - Fee Related CN102522210B (en) | 2011-11-16 | 2011-11-16 | Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102522210B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418148A (en) * | 2011-11-17 | 2012-04-18 | 东南大学 | Titanium dioxide-based polypyrrole jacket nanotube array as well as preparation method and energy storage application thereof |
| CN103343372B (en) * | 2013-07-10 | 2016-09-28 | 四川农业大学 | Solely stand in Polyglycolic acid fibre nano-tube array and pipe nano wire film and its preparation method and application |
| CN105412936B (en) * | 2015-12-23 | 2018-03-27 | 中南大学 | A kind of stimuli responsive type polypyrrole nanotube target medicine carrier and preparation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100521457B1 (en) * | 2002-04-15 | 2005-10-12 | 주식회사 엘지화학 | Electropolymerization method for preparing nano-tube type conducting polymer using porous template, method for preparing electrochromic device, and electrochromic device prepared therefrom |
| US20060289351A1 (en) * | 2004-07-02 | 2006-12-28 | The University Of Chicago | Nanostructures synthesized using anodic aluminum oxide |
| KR100955881B1 (en) * | 2007-09-13 | 2010-05-06 | 고려대학교 산학협력단 | Method for controlling luminescent characteristics of double walled nanotubes |
| CN101550239B (en) * | 2009-05-12 | 2011-08-31 | 厦门大学 | Method of preparing polypyrrole micro-/nano-structure with super-hydrophilic |
-
2011
- 2011-11-16 CN CN201110362862.5A patent/CN102522210B/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| Damian Kowalski et.al.Polypyrrole self-organized nanopore arrays formed by controlled electropolymerization in TiO2 nanotube template.《Chem. Commun.》.2010,第46卷8585-8587. * |
| Electrochemically fabricated polypyrrole nanofiber-modified electrode as a new electrochemical DNA biosensor;Kh. Ghanbari et.al;《Biosensors and Bioelectronics》;20080318;第23卷;1825-1831 * |
| Kh. Ghanbari et.al.Electrochemically fabricated polypyrrole nanofiber-modified electrode as a new electrochemical DNA biosensor.《Biosensors and Bioelectronics》.2008,第23卷1825-1831. * |
| Polypyrrole self-organized nanopore arrays formed by controlled electropolymerization in TiO2 nanotube template;Damian Kowalski et.al;《Chem. Commun.》;20101022;第46卷;8585-8587 * |
| 杜洪秀 等.聚吡咯-二氧化钛纳米复合材料的制备及其电化学性能.《中国科技论文在线》.2011,1-7. * |
| 聚吡咯-二氧化钛纳米复合材料的制备及其电化学性能;杜洪秀 等;《中国科技论文在线》;20110808;1-7 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102522210A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104240967B (en) | Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof | |
| CN104616905B (en) | Polyaniline carbon-coating titanium nitride nano linear array composite and its preparation method and application | |
| CN103840145B (en) | A kind of preparation method of lithium-sulfur cell nano-tube array positive electrode | |
| CN105047423B (en) | A kind of flexibility symmetric form fake capacitance ultracapacitor and preparation method thereof | |
| CN102418148A (en) | Titanium dioxide-based polypyrrole jacket nanotube array as well as preparation method and energy storage application thereof | |
| CN101781788B (en) | Method for preparing specially-shaped titanium dioxide nano-tube films | |
| CN104485234A (en) | Method for preparing flexible super capacitor based on textile fibers and electrodeposited polypyrrole | |
| CN103426649A (en) | Preparation method for different carbon fibers / cobalt hydroxide electrode and solid-liquid composite electrode system | |
| CN102938331A (en) | Foam nickel-base MnO2/C composite electrode material and preparation method thereof | |
| CN102522210B (en) | Polypyrrole nano-tube embedded nano-pore array material as well as preparation method and energy storage application thereof | |
| CN107316752A (en) | A kind of preparation method of the grapheme modified paper capacitor electrode of manganese bioxide/carbon nano tube | |
| CN103123870A (en) | Nanocomposite film electrode material for supercapacitor and producing method thereof | |
| CN104465117A (en) | ZnCo2O4@MnO core-shell heterostructure nanotube array material, and preparation method and application thereof | |
| CN102220619A (en) | Preparation method of nano platinum-nickel duplex metal/titanium dioxide nanotube array composition material | |
| Du et al. | Preparation of a flexible polypyrrole nanoarray and its capacitive performance | |
| CN107195470B (en) | The nanotube-shaped composite material and preparation method of nickel cobalt iron ternary metal oxide | |
| CN103337381A (en) | Method for fabricating flexible electrode | |
| CN106971860A (en) | A kind of MnO2The preparation method of@graphene fiber super capacitor electrode materials | |
| CN102517638B (en) | Polypyrrole ordered nanopore array material as well as preparation method and energy storage application thereof | |
| CN105655139A (en) | Molybdenum oxide/carbon-coated titanium nitride nanotube array composite material and preparation method and application thereof | |
| CN102505124B (en) | Polypyrrole nanocolumn embedded nanoporous array material, preparation method thereof and energy storage application thereof | |
| CN104465121A (en) | Graphene oxide-polyaniline composite electrode material with three-dimensional structure and manufacturing method thereof | |
| CN103343372B (en) | Solely stand in Polyglycolic acid fibre nano-tube array and pipe nano wire film and its preparation method and application | |
| CN105449225A (en) | Preparation method of aluminum collector in three-dimensional porous structure | |
| CN103956272A (en) | Composite plane electrode based on super capacitor diaphragm, 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 | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Jiangning District of Tangshan street in Nanjing city of Jiangsu Province, 211131 soup Road No. 18 Applicant after: Southeast University Address before: 211189 Jiangsu Road, Jiangning Development Zone, Southeast University, No. 2, No. Applicant before: Southeast University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 211189 Jiangsu Road, Jiangning Development Zone, Southeast University, No. 2, No. Patentee after: Southeast University Address before: Jiangning District of Tangshan street in Nanjing city of Jiangsu Province, 211131 soup Road No. 18 Patentee before: Southeast University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141119 Termination date: 20171116 |