CN102522210A - 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
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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 ultracapacitor electrochemistry stored energy application, belong to polymeric material field.
Background technology
Conducting polymer has non-localized pi-electron conjugated system; Possesses certain conductivity through behind the ion doping; It had both had metal and semi-conductive conductive characteristic; The lightweight, flexibility and the machinable characteristic that have kept polymer 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 its good chemical stability, the back high conductivity of mixing, be easy to synthetic and advantage such as pattern is adjustable.In the electrochemical energy storage application, the microstructure features of electric polypyrrole electrode material is even more important, and the 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 specific power of electrode material.So far; The existing report of polypyrrole nano particle, nanometer film and nano wire with single nanostructure characteristic; The polypyrrole nano structure electrode material that aligns has good conductivity and mechanical strength; Both improved the effective ratio area of polypyrrole; Help reactive ion diffusion and electric transmission again, and the synthetic polypyrrole composite nanostructure electrode material that aligns of design can further improve its electrochemistry accumulate performance, thereby in supercapacitor applications, have good prospect.Polypyrrole nanotube embedding nanometer pore array material of the present invention is based on that the polypyrrole nanotube embeds in the polypyrrole nano-pore and the proper alignment that forms, evenly distributes and have micro-structural flexibility and the regulatable a kind of polypyrrole composite nanostructure array material of pattern, can be used as the application that electrode material for super capacitor carries out the electrochemistry high-efficiency energy-storage.
Summary of the invention
The present invention provides a kind of polypyrrole nanotube embedding nanometer pore array material and preparation method thereof, and the present invention provides a kind of polypyrrole nanotube embedding nanometer pore array material to 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: the polypyrrole matrix; On the polypyrrole matrix, be provided with and be the penetrating nano-pore of array distribution and two ends; Be embedded in the polypyrrole nanotube at nano-pore, be provided with the gap between polypyrrole nanotube outer wall and the nano-pore inwall.
The preparation method of polypyrrole nanotube embedding nanometer pore array material of the present invention; At first; In two electrode electro Chemical reaction systems, the titanium sheet is as anode and as work electrode, and platinized platinum is as negative electrode and as auxiliary electrode; The aqueous solution with ammonium fluoride, phosphoric acid and ethylene glycol is the reaction electrolyte solution; Adopt constant voltage anodic oxidation reactions method, that the preparation tube wall is spaced apart, in order and by the titania nanotube of arrayed, the titanium dioxide ordered nano-tube that the tube wall that obtains is spaced apart is as template; Then; In the three-electrode electro Chemical reaction system; Template is as the electrode matrix material and as work electrode; Platinized platinum is as auxiliary electrode; Saturated calomel electrode is as reference electrode, serves as the reaction electrolyte solution with the second cyanogen organic solution of pyrrole monomer and lithium perchlorate, adopts the electric polymerization reaction method of regulation and control; Make polypyrrole be overlying on the polypyrrole nanometer film on the titania nanotube outside wall surface depositing and form complete packet on titanium dioxide ordered nano-tube outside wall surface and the internal face successively, obtain by titania nanotube, be coated on the polypyrrole nanometer film on the 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 the nanotube internal face is composited; At last, be precursor with polypyrrole cladding titanium dioxide nano pipe composite array material, adopt chemical corrosion solubilizing reaction method to remove titanium dioxide ordered nano-tube template fully, 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) the polypyrrole nanotube embeds fully and forms orderly regular arrangement and equally distributed nano array structure in the polypyrrole nano-pore; Wherein said nano-pore and nanotube all have the penetrating characteristic in two ends, nanotube have the individual tubes wall construction and and the nano-pore wall between keep the characteristic of uniform gap.
(2) polypyrrole nano-pore and polypyrrole nanotube can both provide the nanochannel of complete permeability; And keep uniform gap between nanotube outer wall and the nano-pore inwall; Increased effective ratio area on the one hand; Optimized 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 nano-pore and polypyrrole nanotube have the polypyrrole conducting film of regular orderly arrangement; Electrochemical reaction produces electronics and under electric field action, carries out axial oriented and ordered transmission along the polypyrrole conducting film; Improved electrical conductivity efficient, 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 the precursor material is easy to get, and cost of material is cheap relatively.
Description of drawings
Fig. 1 is the micro-structural sketch map 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 prepares polypyrrole cladding titanium dioxide nano pipe composite array material.
Fig. 9 is that the regular circulation voltammetry is carried out the ESEM front plan view that electric polymerization reaction prepares 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 prepares polypyrrole-titanium dioxide composite nano-tube material.
Embodiment
Through specific embodiment, the preparation method and the electrode of super capacitor electrochemical energy storage thereof that further specify polypyrrole nanotube embedding nanometer pore array material are used below.
The preparation method of polypyrrole ordered nano hole array material of the present invention may further comprise the steps.
(1) synthesizes the titanium dioxide ordered nano-tube template that tube wall is spaced apart
At first, the pure titanium sheet of metal is cleaned 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, the titanium sheet is as anode and as work electrode; Platinized platinum is as negative electrode and as auxiliary electrode, serves as the reaction electrolyte solution with the aqueous solution of 0.2mol/L ammonium fluoride, 0.5mol/L phosphoric acid and 9.0mol/L ethylene glycol, and the setting constant voltage is 30V; Reaction time is 2h; Reaction temperature is 20-25 ℃, adopts constant voltage anodic oxidation reactions method, and is that the preparation tube wall is spaced apart, in order and by the titania nanotube of arrayed; The titanium dioxide ordered nano-tube that the tube wall that obtains is spaced apart is as template, and described template has the architectural feature that uniform gap is arranged between the nanotube tube wall; At last, titanium dioxide ordered nano-tube template is fully washed with deionized water, dries naturally, and carries out the heat treatment of 450 ℃ of roasting 2h, and template is converted into anatase phase crystal by amorphous amorphous state.
(2) synthetic polypyrrole nanotube embedding nanometer pore array material
At first, the titanium dioxide ordered nano-tube template with above-mentioned preparation immerses sonic oscillation processing 30-60min in the pyrrole monomer; Then, in the 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 a work electrode, and platinized platinum is an auxiliary electrode, and saturated calomel electrode is a reference electrode; Second cyanogen solution with 0.18mol/L lithium perchlorate and 0.15mol/L pyrrole monomer is the reaction electrolyte solution, and the take-off potential that pulse voltammetry is set on the work electrode is 0.7V, and the termination current potential is 1.1V; The current potential increment is 0.001V/s; The sampling time width is 0.02s, and pulse duration is 0.06s, and the pulse period is 4s.The electric polymerization reaction that adopts pulse voltammetry to regulate and control; Make polypyrrole be overlying on the polypyrrole nanometer film on the nanotube tube wall face depositing and form complete packet on titanium dioxide ordered nano-tube outside wall surface and the internal face successively, obtain by titania nanotube, be coated on the polypyrrole nanometer film on the 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 the nanotube internal face is composited.At last, adopt chemical corrosion solubilizing reaction method, polypyrrole cladding titanium dioxide nano pipe composite array material is removed titanium dioxide ordered nano-tube template fully in hydrofluoric acid aqueous solution, obtain described polypyrrole nanotube embedding nanometer pore array material.The hydrofluoric acid molar concentration is 2.0mol/L, titanium dioxide corrosion dissolution reaction 30min.
The 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: the polypyrrole nanotube embeds fully and forms orderly regular arrangement and equally distributed nano array structure in the polypyrrole nano-pore; Wherein said nano-pore and nanotube all have the penetrating characteristic in two ends; Nanotube have the individual tubes wall construction and and the nano-pore wall between keep the characteristic of uniform gap; The nano-pore diameter range is 115-225nm; The nano-pore length range is 700-1300nm, and the clearance distance scope between polypyrrole nanotube outer wall and the nano-pore inwall is 15-45nm, sees Figure of description 2 and 3 for details.Figure of description 4 is ESEM profiles of polypyrrole nanotube embedding nanometer pore array material; I is the side partly cut-away zone of polypyrrole nanotube embedding nanometer pore array material among the figure; All include a polypyrrole nanotube in each polypyrrole nano-pore; Keep uniform gap between nanotube outside wall surface and the nano-pore internal face, and the complete conducting of nanotube zone line, this shows; Polypyrrole nanotube embedding nanometer pore array material has the nanochannel characteristic of complete conduction, and nanotube embeds nano-pore and forms the 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 all is shown as the eigen vibration peak of polypyrrole; The eigen vibration peak that titanium dioxide do not occur; Synthetic sample is the polypyrrole nanotube embedding nanometer pore array material that removes titanium dioxide ordered nano-tube template fully, sees Figure of description 5 for details.
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 following 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; With the 1.0M lithium perchlorate aqueous solution is Working electrolyte; Polypyrrole nanotube embedding nanometer pore array material is a work electrode, and platinized platinum is an auxiliary electrode, and saturated calomel electrode is a reference electrode; Adopt electrochemical workstation (IM6e; ZAHNER Elektrik Germany) carries out constant current cycle charge discharge electrical testing, and the constant current density of setting the cycle charge discharge electrical testing is 0.25mA/cm
2, calculating electrochemical capacitor according to constant current cycle charge-discharge test data of experiment, the area specific capacitance of polypyrrole nanotube embedding nanometer pore array material is 16.67mF/cm
2, see Figure of description 6 for details.
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 prepares 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 the adjacent nanotube is higher than the conductivity of the tube chamber inner region of nanotube, and 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 more to help pyrrole monomer and carry out the directed diffusive migration and the electric polymerization reaction of location.It is following that pulse voltammetry of the present invention is set Control Parameter: the second cyanogen organic solution with pyrrole monomer and lithium perchlorate serves as in the reaction electrolyte solution; The molar concentration of pyrrole monomer is 0.15mol/L, and the molar concentration scope of lithium perchlorate is 0.15mol/L, and the take-off potential of work electrode is 0.7V; The termination current potential is 1.1V; The current potential increment is 0.001V/s, and pulse duration is 0.06s, and the 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; Make polypyrrole be overlying on the polypyrrole nanometer film on the nanotube tube wall face depositing and form complete packet on titanium dioxide ordered nano-tube outside wall surface and the internal face successively; Obtain by titania nanotube, be coated on the polypyrrole nanometer film on the 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 the 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 sketch map are with reference to Figure of description 1, and 1 representes the polypyrrole matrix among the figure; 2 expression nano-pores among the figure, 2 expression polypyrrole nanotubes among the figure, 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, be provided with the gap between polypyrrole nanotube 3 outer walls and nano-pore 2 inwalls, the diameter range of nano-pore 2 is 115-225nm; The length range of nano-pore 2 is 700-1300nm, and the distance range in gap is 15-45nm.
Reference examples 1
This reference examples is to adopt the regular circulation voltammetry to carry out the electric polymerization reaction method to prepare polypyrrole-titanium dioxide composite nano-tube material.
Adopt the regular circulation voltammetry to carry out electric polymerization reaction and prepare polypyrrole-titanium dioxide composite nano tube; Described regular circulation voltammetry setup parameter is following: the second cyanogen solution with molar concentration 0.15mol/L pyrrole monomer and molar concentration 0.10mol/L lithium perchlorate is the 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 the 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 zone on the titania nanotube mouth of pipe or surface; With reference in the Figure of description 9 shown in the II; Another part zone on the titania nanotube mouth of pipe or surface does not form polypyrrole nanometer film cover layer; With reference in the Figure of description 9 shown in the III, in the tube wall face of titania nanotube and tube chamber, all do not form the polypyrrole nanometer film.This shows; Adopt the regular circulation voltammetry to carry out electric polymerization reaction; Polypyrrole can't be regulated 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 can't be formed, thereby polypyrrole nanotube embedding nanometer pore array material can't be prepared.
Reference examples 2
This reference examples is to adopt conventional potentiostatic method to carry out the 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 following: the second cyanogen solution of molar concentration 0.15mol/L pyrrole monomer and molar concentration 0.10mol/L lithium perchlorate is the 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 the polypyrrole nano particle at the surf zone of titania nanotube; All do not form the polypyrrole nanometer film in the tube wall face of nanotube and the tube chamber, with reference to Figure of description 10.This shows; Adopt conventional potentiostatic method to carry out electric polymerization reaction; Polypyrrole can't be regulated 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 can't be formed, thereby polypyrrole nanotube embedding nanometer pore array material can't be prepared.
Claims (7)
1. polypyrrole nanotube embedding nanometer pore array material; It is characterized in that: 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), be provided with the gap between polypyrrole nanotube (3) outer wall and nano-pore (2) inwall.
2. polypyrrole nanotube embedding nanometer pore array material according to claim 1, it is characterized in that: the diameter range of described nano-pore (2) is 115-225nm, and the length range of nano-pore (2) is 700-1300nm, and the distance range in gap is 15-45nm.
3. the preparation method of polypyrrole nanotube embedding nanometer pore array material according to claim 1; It is characterized in that: at first; In two electrode electro Chemical reaction systems, the titanium sheet is as anode and as work electrode, and platinized platinum is as negative electrode and as auxiliary electrode; The aqueous solution with ammonium fluoride, phosphoric acid and ethylene glycol is the reaction electrolyte solution; Adopt constant voltage anodic oxidation reactions method, that the preparation tube wall is spaced apart, in order and by the titania nanotube of arrayed, the titanium dioxide ordered nano-tube that the tube wall that obtains is spaced apart is as template; Then; In the three-electrode electro Chemical reaction system; Titanium dioxide ordered nano-tube template is as the electrode matrix material and as work electrode; Platinized platinum is as auxiliary electrode; Saturated calomel electrode is as reference electrode, serves as the reaction electrolyte solution with the second cyanogen organic solution of pyrrole monomer and lithium perchlorate, adopts the electric polymerization reaction method of regulation and control; Make polypyrrole be overlying on the polypyrrole nanometer film on the nanotube tube wall face depositing and form complete packet on titanium dioxide ordered nano-tube outside wall surface and the internal face successively, obtain by titania nanotube, be coated on the polypyrrole nanometer film on the 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 the nanotube internal face is composited; At last, be precursor with polypyrrole cladding titanium dioxide nano pipe composite array material, adopt chemical corrosion solubilizing reaction method to remove titanium dioxide ordered nano-tube template fully, obtain polypyrrole nanotube embedding nanometer pore array material.
4. preparation method according to claim 3; It is characterized in that: described constant voltage anodic oxidation reactions method is: the setting constant voltage is 30V, and the reaction time is 2h, and reaction temperature is 20-25 ℃; The aqueous solution with ammonium fluoride, phosphoric acid and ethylene glycol serves as in the reaction electrolyte solution; The ammonium fluoride molar concentration is 0.2mol/L, and the phosphoric acid molar concentration is 0.5mol/L, and the ethylene glycol molar concentration is 9.0mol/L.
5. preparation method according to claim 3 is characterized in that: the electric polymerization reaction method of regulation and control adopts pulse voltammetry, and described pulse voltammetry is: the take-off potential that is set on the work electrode is 0.7V; The termination current potential is 1.1V; The current potential increment is 0.001V/s, and the sampling time width is 0.02s, and pulse duration is 0.06s; The pulse period scope is 3-6s; Second cyanogen organic solution with pyrrole monomer and lithium perchlorate serves as that the molar concentration of pyrrole monomer is 0.15mol/L in the reaction electrolyte solution, and the molar concentration scope of lithium perchlorate is 0.15-0.20mol/L.
6. preparation method according to claim 3; 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: be immersed in polypyrrole cladding titanium dioxide nano pipe composite array material in the hydrofluoric acid aqueous solution fully; Titanium dioxide generation chemical corrosion solubilizing reaction; Obtain described polypyrrole nanotube embedding nanometer pore array material after removing template fully, titanium dioxide corrosion dissolution reaction time range is 20-40min, and hydrofluoric acid molar concentration scope is 1.5-2.5mol/L.
7. polypyrrole nanotube embedding nanometer pore array material according to claim 1 carries out the application of electrochemical energy storage as electrode material for super capacitor.
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| 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 |
| CN103343372A (en) * | 2013-07-10 | 2013-10-09 | 四川农业大学 | Poly (3,4-ethylenedioxythiophene) nano-tube array and tube independent standing nano-wire film, as well as preparation method and 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 |
| CN105412936A (en) * | 2015-12-23 | 2016-03-23 | 中南大学 | Stimulus-response type polypyrrole nanotube targeting drug carrier and preparation method |
| 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 |
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