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.
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.