CN104112603A - Polypyrrole-titanium dioxide or titanium nitride-polyaniline coaxial three-layer nanotube array composite material, and preparation method and application thereof - Google Patents
Polypyrrole-titanium dioxide or titanium nitride-polyaniline coaxial three-layer nanotube array composite material, and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 271
- 239000002071 nanotube Substances 0.000 title claims abstract description 203
- 239000002131 composite material Substances 0.000 title claims abstract description 177
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 139
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims description 103
- 239000010936 titanium Substances 0.000 title claims description 103
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 29
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 51
- 230000008021 deposition Effects 0.000 claims abstract description 27
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 109
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000126 substance Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 150000003233 pyrroles Chemical class 0.000 claims description 27
- 239000008151 electrolyte solution Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000004832 voltammetry Methods 0.000 claims description 22
- 238000003487 electrochemical reaction Methods 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 15
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 15
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- 235000019394 potassium persulphate Nutrition 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LWUAMROXVQLJKA-UHFFFAOYSA-N 2-amino-3-chlorobenzoic acid Chemical compound NC1=C(Cl)C=CC=C1C(O)=O LWUAMROXVQLJKA-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- -1 allyl ester Chemical class 0.000 claims description 10
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004220 aggregation Methods 0.000 claims description 8
- 230000002776 aggregation Effects 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 16
- 229920001940 conductive polymer Polymers 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 5
- 239000002019 doping agent Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000008602 contraction Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 30
- 239000000178 monomer Substances 0.000 description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002322 conducting polymer Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005915 ammonolysis reaction Methods 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a coaxial three-layer nanotube array composite material. The coaxial three-layer nanotube array composite material comprises a titanium dioxide or titanium nitride nanotube array frame, a polypyrrole nanotube formed through polymeric deposition at the outer wall surface of the frame, and a polyaniline nanotube formed through polymeric deposition at the inner wall surface of the frame. The invention also provides a preparation method of the coaxial three-layer nanotube array composite material and an electrochemical energy storage application of the coaxial three-layer nanotube array composite material. The composite material is prepared by taking a titanium dioxide or titanium nitride nanotube as the frame, the frame is of a hollow structure, has uniform tube spacing and can absorb volume contraction and expansion caused when a conductive polymer is charged and discharged, and the circulating life of an electrode material is prolonged; the multi-gap hollow tubular structure enables polyaniline and polypyrrole to be fully contacted with a doping agent electrolyte, such that ion diffusion and charge transfer are facilitated; and the composite material comprises P-type doped characteristic polypyrrole and n-type doped characteristic polypyrrole at the same time and fully utilizes anions and cations in a solution so as to obtain a super capacitor electrode material with high specific capacitance and good circulating stability.
Description
Technical field
The invention belongs to electrochemical material field, relate to a kind of coaxial three layers of nanotube array composite material, be particularly related to a kind of polypyrrole-titanium dioxide-polyaniline or polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure, more particularly, a kind of by titanium dioxide or titanium nitride nano cannon born frame, the conductive doped polymer poly pyrroles of N-shaped nanotube, the conductive doped polymer polyaniline nanotube of p-type ordered fabrication forms coaxial three layers of nanometer tube composite materials, also relate to the preparation method of these coaxial three layers of nanotube array composite materials and the application in electrochemical energy storage field.
Background technology
Ultracapacitor is the Novel energy storage apparatus of a kind of performance between dielectric capacitor and battery, and this device has the advantages such as charge-discharge velocity is fast, specific capacity large, have extended cycle life, the fields such as extensive use and portable electric appts, hybrid vehicle.Electrode material is the most key part of ultracapacitor, is also to determine the principal element of its performance, and therefore to have the electrode material of excellent accumulate performance be most crucial content in ultracapacitor research in exploitation.
Conducting polymer is the important electrode material for super capacitor of a class, and its accumulate performance mainly comes from pseudo capacitance.Conducting polymer claims again conducting polymer, has large conjugated pi system in this family macromolecule structure, by means such as doping, realizes the transfer of electric charge and flows and realize conduction with the form of pi-electron in conjugated pi system.Common conducting polymer has: polyacetylene, polypyrrole, polyaniline, polythiophene and derivative thereof etc.Electric polypyrrole is the conductive doped polymer of typical p-type, conventional anion doped dose has lithium perchlorate, sulfonic dopants, inorganic acid dopant etc., and polypyrrole has high conductivity after good chemical stability, doping, is easy to synthesize, pattern is in advantages such as regulation and control.Electrically conductive polyaniline has unique Bronsted acid/cation doping mechanism, and conventional cation acid dopant is various organic Bronsted acids and inanimate matter acid.Polyaniline conductivity is good, has the advantages such as monomer low price, high charge density, is one of the most potential kind in conducting polymer composite.In same electrode material for super capacitor, introduce the polypyrrole active material of p-type doping and the polyaniline active material of N-shaped doping simultaneously, in capacitor charging/discharging process, two kinds of active materials participate in the charge transfer process of ion doping simultaneously, can make full use of zwitterion in electrolyte, improve the accumulate performance of electrode material.
At present, had much about the method for polypyrrole and polyaniline electrode material of preparing different-shape.Such as the liquid-liquid interface that utilizes polyaniline and polypyrrole monomer to form, adopt electrochemical polymerization to prepare polyaniline and composite polypyrrole film, but the common structural disorder of the polymer film that this preparation method obtains and less with the contact area of electrolyte, is unfavorable for making full use of of two kinds of conducting polymer physical performances.
Summary of the invention
Goal of the invention: the invention provides a kind of polypyrrole-titanium dioxide-polyaniline of three layers of nano-tube array structure of Novel coaxial that N-shaped doping and p-type doping occur simultaneously or polypyrrole-titanium nitride-polyaniline composite electrode material and preparation method thereof, and apply as the electrochemical energy storage of ultracapacitor, secondary battery electrode material.
Technical scheme: the coaxial three layers of nanotube array composite material of a kind of polypyrrole-titanium dioxide provided by the invention or titanium nitride-polyaniline, is characterized in that: the polypyrrole nanotube (2) that comprise the titanium dioxide of pipe wall absolute construction or titanium nitride nano pipe array skeleton (1), forms at titanium dioxide or titanium nitride nano pipe array skeleton (1) outside wall surface aggregation deposition and the polyaniline nanotube (3) forming at titanium dioxide or titanium nitride nano pipe array skeleton (1) internal face aggregation deposition; The coaxial three layers of nanotube array composite material of described polypyrrole-titanium dioxide or titanium nitride-polyaniline are one group of array structure with the tight ordered arrangement formation of three layers of nanotube of concentric shafts, described three layers of nanotube with concentric shafts are outer is polypyrrole nanotube, intermediate layer is titanium dioxide or titanium nitride nano pipe, and internal layer is polyaniline nanotube.
The coaxial three layers of nanotube array composite material of described polypyrrole-titanium dioxide or titanium nitride-polyaniline are incorporated into conductive doped p-type polymer poly pyrroles and the conductive doped polymer poly aniline of N-shaped respectively outside wall surface and the internal face of titanium dioxide or titanium nitride nano cannon born frame, have formed the composite material of p-n junction heterojunction polymer features.
Preferably, the pipe thickness of titanium dioxide or titanium nitride nano pipe is that 10-20nm, internal diameter are that 80-130nm, length are 860-960nm, and between adjacent titanium dioxide or titanium nitride nano pipe, distance is 30-68nm; In the time that skeleton is Nano tube array of titanium dioxide, the pipe thickness of polypyrrole nanotube is 8-15nm, and the pipe thickness of polyaniline nanotube is 8-11nm; In the time that skeleton is titanium nitride nano pipe array, the pipe thickness of polypyrrole nanotube is 18-30nm, and the pipe thickness of polyaniline nanotube is 5-15nm.
The present invention also provides the preparation method of above-mentioned a kind of polypyrrole-titanium dioxide or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, help the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprise the following steps:
(1) preparation of Nano tube array of titanium dioxide: adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, using titanium sheet as anode and as work electrode, using platinized platinum as negative electrode and as assisting electrode, using the mixed aqueous solution of ammonium fluoride, phosphoric acid, methyl alcohol and ethylene glycol as reaction electrolyte solution, under constant voltage 20-30V condition, react 1-3h, make the Nano tube array of titanium dioxide of amorphous state; The Nano tube array of titanium dioxide of amorphous state, at 400-500 DEG C of high-temperature calcination 1-3h, is made to the Nano tube array of titanium dioxide of Anatase;
(2) preparation of titanium nitride nano pipe array: step (1) makes the Nano tube array of titanium dioxide of Anatase under pure ammonia atmosphere condition, and 900 DEG C of constant temperature nitrogen treatment 1-2h, make titanium nitride nano pipe array;
(3) preparation of the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization: the titanium nitride nano pipe array surface that the Nano tube array of titanium dioxide that step (1) is made or step (2) make is evenly smeared the carbonic allyl ester solution of pyrroles and ferric trichloride, under vacuum condition, 35-45 DEG C of constant temperature is processed 6-8min, repeat 3-5 time, obtain the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization;
(4) preparation of polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization as work electrode, using the propene carbonate mixed solution of pyrroles, lithium perchlorate and methyl alcohol as reaction electrolyte solution, adopt step scanning voltammetry electrochemical polymerization reaction to make polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material;
(5) preparation of the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization: polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material that step (4) is made soak after 5-15min in the acetonitrile solution of aniline, potassium peroxydisulfate, be inverted in hydrothermal reaction kettle, 55-65 DEG C of incubation water heating processed 1-2h, makes the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization;
(6) preparation of coaxial three layers of nanotube array composite material: in three-electrode electro Chemical reaction system, pretreated polypyrrole-titanium dioxide-the polyaniline composite material of chemical polymerization making taking step (5) or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization are as work electrode, using aniline, chloro-2 amino benzoic Acid of 4-and the dimethyl formamide aqueous solution as reaction electrolyte solution, under 1000W xenon lamp irradiates, adopt step scanning voltammetry light to help electrochemical polymerization reaction to make coaxial three layers of nanotube array composite material.
In step (1), in reaction electrolyte solution, the molar concentration of ammonium fluoride is that the molar concentration of 0.15-0.30mol/L, phosphoric acid is 0.4-0.5mol/L, and the volume fraction of methyl alcohol is that the volume fraction of 5-8%, ethylene glycol is 35-45%; Preferably, the molar concentration of ammonium fluoride is that the molar concentration of 0.2mol/L, phosphoric acid is that the volume fraction of 0.5mol/L, methyl alcohol is 5%, the volume fraction of ethylene glycol is 40%.
In step (2), pure ammonia atmosphere environment is: ammonia concentration is 99.0-99.6%, and ammonia flow is 30-50mL/min; 900 DEG C of constant temperature nitrogen treatment programs are: be warming up to 900 DEG C of constant temperature and process 1-2h; Heating schedule is: be 5 DEG C/min from room temperature to 300 DEG C, from 300 to 700 DEG C is 2 DEG C/min, and from 700 to 900 DEG C is 1 DEG C/min.
In step (3), in the carbonic allyl ester solution of pyrroles and ferric trichloride, pyrroles's molar concentration is 0.5-1.5mol/L, preferably 1.0mol/L, and the molar concentration of ferric trichloride is 0.025-0.030mol/L, preferably 0.028mol/L.
In step (4), in the propene carbonate mixed solution of pyrroles, lithium perchlorate and methyl alcohol, pyrroles's molar concentration is 0.15-0.25mol/L, and the molar concentration of lithium perchlorate is 0.05-0.1mol/L, the volume fraction 3-5% of methyl alcohol; Preferably, pyrroles's molar concentration is 0.2mol/L, and the molar concentration of lithium perchlorate is 0.075mol/L, the volume fraction 4% of methyl alcohol; Step scanning voltammetry condition is: take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is 0.001-0.004V/s, and the step cycle is 0.1-0.4s, and scanning hop count is 3-6.
In step (5), in the acetonitrile solution of aniline, potassium peroxydisulfate, the molar concentration of aniline is that the molar concentration of 0.05-0.15mol/L, potassium peroxydisulfate is 0.04-0.06mol/L, and preferably, the molar concentration of aniline is that the molar concentration of 0.10mol/L, potassium peroxydisulfate is 0.05mol/L.
In step (6), in aniline, the chloro-amino benzoic Acid of 4-and the dimethyl formamide aqueous solution, the molar concentration of aniline is that the molar concentration of chloro-2 amino benzoic Acid of 0.05-0.2mol/L, 4-is that the volume fraction of 0.3-0.5mol/L, dimethyl formamide is 5-10%; Step scanning voltammetry condition is: take-off potential is-0.2V, and termination current potential is 1.0V, and current potential increment is 0.001-0.004V/s, and the step cycle is 0.2-0.8s, and scanning hop count is 5-10.Application in the coaxial three layers of nanotube array composite material electrochemical energy storage field of a kind of polypyrrole-titanium dioxide described in claim 1-2 any one or titanium nitride-polyaniline.
The present invention also provides polypyrrole-titanium dioxide or the application of the coaxial three layers of nanotube array composite material of polypyrrole-titanium nitride in electrochemical energy storage field, be specially: above-mentioned coaxial three layers of nanotube array composite material are applied in ultracapacitor to the sulfuric acid (H that working electrolyte is liquid phase as positive and negative electrode material
2sO
4), phosphoric acid (H
3pO
4), perchloric acid (HClO
4) lithium perchlorate-phosphoric acid-polyvinyl alcohol (LiClO of the aqueous solution or solid-state phase
4-H
3pO
4-PVA) gel.
Beneficial effect: coaxial three layers of nanotube array composite material provided by the invention make taking titanium dioxide or titanium nitride nano pipe array as skeleton, titanium dioxide or titanium nitride nano pipe are not only for deposited polymer provides orderly skeleton, and its hollow structure and uniformly tube pitch can absorb the volume contraction and the expansion that when conducting polymer discharges and recharges, cause, thereby the cycle life of intensifier electrode material; Lacunose hollow tubular structure makes polyaniline fully contact with dopant electrolyte with polypyrrole, being conducive to electrolyte ion diffusion shifts with electric charge, composite materials comprises p-type doping characteristic polypyrrole and N-shaped doping characteristic polyaniline simultaneously, make full use of yin, yang ion in solution, thereby obtain the electrode material for super capacitor of high specific capacitance, good cycling stability.
Particularly, the present invention, with respect to prior art, has following outstanding advantage:
(1) coaxial three layers of nanotube array composite material provided by the invention are formed by polypyrrole nanotube, titanium dioxide or titanium nitride nano pipe and polyaniline nanotube successively ordered fabrication respectively, have the conductive doped polymer of p-type and the conductive doped polymer of N-shaped concurrently, in cycle charge discharge electric process, can be simultaneously with mate electrolytic anion, cation generation p-type is adulterated and N-shaped doping reaction, has high specific capacitance value and good circulation stability concurrently.
(2) preparation method of coaxial three layers of nanotube array composite material provided by the invention, utilizes the tube pitch of nanotube and the polymerization activity otherness of pipe interface stress otherness, pyrroles and aniline monomer to realize the selective polymerisation reactive deposition of regulation and control.Polypyrrole adopts the preliminary treatment of chemical polymerization nucleation and the electrochemical polymerization reactive deposition under vacuum condition to form polyaniline nanotube, polyaniline adopts the preliminary treatment of chemical polymerization nucleation and the light under hydrothermal condition to help electrochemical polymerization reactive deposition to form polypyrrole nanotube, and optionally substep, subregion deposit on titanium dioxide or titanium nitride skeleton to have regulated and controled well these two kinds of polymer of polypyrrole and polyaniline.Electric polymerization reaction synthetic method has adopted step scanning voltammetry, than methods such as the cyclic voltammetry of general employing, galvanostatic method, potentiostatic methods, step scanning voltammetry can better be controlled polymerization reaction, makes polypyrrole preferentially in the pipe outside wall surface deposition at titanium dioxide or titanium nitride nano pipe.
(3) coaxial three layers of nanotube array composite material are applied to super capacitor function electrode, N-shaped conducting polymer polypyrrole and p-type electric-conducting polymer poly aniline in titanium dioxide or titanium nitride nano cannon born frame, have been introduced simultaneously, in electrochemistry cycle charge discharge electric process, two kinds of conducting polymer whiles are carried out doping reaction with anion and cation in electrolyte solution, improve the electric charge rate of transform, increased the electrochemical energy storage performance of electrode material.Coaxial three layers of nano-tube array structure are not only conducive to electrode active material and fully contact with electrolyte, reduce charge transfer resistance, and the structure of hollow can also absorb the volume contraction and the expansion that cause when macromolecular material discharges and recharges, thus the cycle life of intensifier electrode material.The ratio electric capacity of the polypyrrole-titanium dioxide-polyaniline composite material of described coaxial three layers of nano-tube array structure can reach 450-600F/g, and cycle life can arrive above (capacitance conservation rate is 75-85%) 1000 times; The ratio electric capacity of the polypyrrole-titanium nitride-polyaniline composite material of described coaxial three layers of nano-tube array structure can reach 1800-2000F/g, and cycle life can arrive above (capacitance conservation rate is 81-91%) 1000 times.As can be seen here, coaxial three layers of nanotube array composite material provided by the invention have higher specific volume value and good cyclical stability, are the active electrode materials of high-efficiency energy-storage type, have very wide application prospect.
Brief description of the drawings
Fig. 1 is the structural representation of the coaxial three layers of nanotube array composite material of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of titanium dioxide or titanium nitride nano pipe, and wherein (a) is front elevation, is (b) side view.
Fig. 3 is the scanning electron microscope (SEM) photograph of polypyrrole-composite titania material, and wherein (a) front elevation, (b) is side view.
Fig. 4 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium dioxide-polyaniline composite material, and wherein (a) is front elevation, is (b) side view.
Fig. 5 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium nitride composite material, and wherein (a) is front elevation, is (b) side view.
Fig. 6 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium nitride-polyaniline composite material, and wherein (a) is front elevation, is (b) side view.
Fig. 7 is (a) titania nanotube, (b) polypyrrole-composite titania material, (c) polyaniline-composite titania material and (d) Raman spectrogram of polypyrrole-titanium dioxide-polyaniline composite material.
Fig. 8 is (a) titanium nitride nano pipe, (b) polypyrrole-titanium nitride composite material, (c) polyaniline-titanium nitride composite material, (d) Raman spectrogram of polypyrrole-titanium nitride-polyaniline composite material.
Fig. 9 be (a) polypyrrole-composite titania material and (b) polypyrrole-titanium dioxide-polyaniline composite material at 0.5mol/L H
2sO
4in solution, the cyclic voltammetry curve under 20mV/s sweep speed condition.
Figure 10 be (a) polypyrrole-composite titania material and (b) polypyrrole-titanium dioxide-polyaniline composite material at 0.5mol/L H
2sO
4in solution, the constant current charge-discharge curve under 0.5A/g current density.
Figure 11 be (a) polypyrrole-titanium dioxide-polyaniline composite material and (b) polypyrrole-titanium nitride-polyaniline composite material at 0.5mol/L H
2sO
4in solution, the cyclic voltammetry curve under 100mV/s sweep speed condition.
Figure 12 be (a) polypyrrole-titanium dioxide-polyaniline composite material and (b) polypyrrole-titanium nitride-polyaniline composite material at 0.5mol/L H
2sO
4in solution, the constant current charge-discharge curve under 1.0A/g current density.
Embodiment
Can have better elaboration to the present invention by the following examples, but these embodiment can not be interpreted as limitation of the scope of the invention.
Embodiment 1
(1) prepare titanium dioxide and titanium nitride nano pipe array framework material: titanium sheet is cleaned to 30min, polishing in the hydrogen fluoride/nitric acid/water solution that is 1:4:5 in volume ratio after taking-up in ethanol, acetone, deionized water for ultrasonic successively; In two electrode electro Chemical reaction systems, titanium sheet is as anode, platinized platinum is as negative electrode, taking the aqueous solution of phosphoric acid, volume fraction 5% methyl alcohol and volume fraction 40% ethylene glycol of the ammonium fluoride of 0.2mol/L, 0.5mol/L as reaction electrolyte solution, adopt anode oxidation method, under constant voltage 30V condition, 25 DEG C of isothermal reaction 2h, then fully rinse and naturally dry afterwards with deionized water, make pipe wall independent, the Nano tube array of titanium dioxide that the mouth of pipe is unlimited.Nano tube array of titanium dioxide is processed in high-temperature calcination, and design temperature is 450 DEG C, and the reaction time is 2h, makes the Nano tube array of titanium dioxide of Anatase; High-temperature ammonolysis is processed Nano tube array of titanium dioxide, setting ammonia concentration is 99.6%, ammonia flow is 50mL/min, reaction temperature is 900 DEG C, reaction time is 1h, and heating rate is: be 5 DEG C/min from room temperature to 300 DEG C, from 300 to 700 DEG C is 2 DEG C/min, from 700 to 900 DEG C is 1 DEG C/min, makes titanium nitride nano pipe array.The scanning electron microscope (SEM) photograph of the scanning electron microscope (SEM) photograph of Nano tube array of titanium dioxide and titanium nitride nano pipe array is basically identical, its front elevation and side view show, pipe thickness is that 10-20nm, internal diameter are that 80-130nm, length are 860-960nm, between adjacent titanium dioxide or titanium nitride nano pipe, distance is 30-68nm, nanotube ordered arrangement, the mouth of pipe opens wide, and pattern is even, sees Figure of description 2.
(2) prepare the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure: the carbonic allyl ester solution of smearing 1.0mol/L pyrroles and 0.028mol/L ferric trichloride as the titania nanotube surface uniform of skeleton, under 40 DEG C of constant temperature and vacuum condition, process 6min, said process repeats 5 times, makes the pretreated polypyrrole-composite titania material of chemical polymerization, in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-composite titania material of chemical polymerization as work electrode, with 0.2mol/L pyrroles, 0.1mol/L lithium perchlorate, the propene carbonate of volume fraction 4% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.001V/s, the step cycle is 0.1s, scanning hop count is 6, pyrrole monomer optionally forms polypyrrole nanotube in titania nanotube outside wall surface homogeneous polymerization deposition, make the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure.Polypyrrole-the composite titania material of described coaxial two layers of nano-tube array structure takes out and is inverted in hydrothermal reaction kettle soak 10min in the acetonitrile solution of 0.1mol/L aniline, 0.05mol/L potassium peroxydisulfate after, under 60 DEG C of constant temperature and hydrothermal condition, process 1h, make the pretreated polypyrrole-titanium dioxide-polyaniline composite material of hydrothermal chemistry polymerization reaction, in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization as work electrode, with 0.2mol/L aniline, chloro-2 amino benzoic Acid of 0.4mol/L4-, the dimethyl formamide of volume fraction 8% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.001V/s, the step cycle is 0.2s, scanning hop count is 8, aniline monomer optionally forms polyaniline nanotube at titania nanotube internal face homogeneous polymerization reactive deposition, make the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
The ESEM front elevation demonstration of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure, polypyrrole is optionally deposited on titania nanotube outside wall surface, and the pipe thickness of polypyrrole nanotube is 8-15nm, sees Figure of description 3.
The ESEM front elevation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure and side view show, polyaniline selectivity is deposited on titania nanotube internal face, the pipe thickness of polyaniline nanotube is 8-11nm, in addition, titania nanotube mouth of pipe deposition forms one deck polyaniline film, its thickness is 20-45nm, sees Figure of description 4.
By the micro-structural of Figure of description 4 known these polypyrrole-titanium dioxide-polyaniline composite materials, structural representation is shown in Fig. 1, taking the Nano tube array of titanium dioxide of pipe wall absolute construction as skeleton, in titania nanotube outside wall surface, aggregation deposition forms polypyrrole nanotube, and aggregation deposition forms polyaniline nanotube on titania nanotube internal face, by Nano tube array of titanium dioxide 1, the polypyrrole nanotube 2 forming in titania nanotube 1 outside wall surface, and the polyaniline nanotube 3 forming on titania nanotube 1 internal face, form together the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
(3) prepare the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure: the carbonic allyl ester solution of evenly smearing 1.0mol/L pyrroles and 0.028mol/L ferric trichloride as the titanium nitride nano pipe array surface of skeleton, under 40 DEG C of constant temperature and vacuum condition, process 6min, said process repeats 5 times, makes the pretreated polypyrrole-titanium nitride composite material of chemical polymerization, in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium nitride composite material of chemical polymerization as work electrode, with 0.2mol/L pyrroles, 0.05mol/L lithium perchlorate, the propene carbonate of volume fraction 4% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.001V/s, the step cycle is 0.1s, scanning hop count is 4, pyrrole monomer optionally forms polypyrrole nanotube in titanium nitride nano pipe outside wall surface homogeneous polymerization deposition, make the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure.Described polypyrrole/titanium nitride composite material takes out and is inverted in hydrothermal reaction kettle soak 10min in the acetonitrile solution of 0.1mol/L aniline, 0.05mol/L potassium peroxydisulfate after, under 60 DEG C of constant temperature and hydrothermal condition, process 1h, make the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization, in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization as work electrode, with 0.1mol/L aniline, chloro-2 amino benzoic Acid of 0.4mol/L4-, the dimethyl formamide of volume fraction 10% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.004V/s, the step cycle is 0.8s, scanning hop count is 6, aniline monomer optionally forms polyaniline nanotube in titanium nitride nano inside pipe wall face homogeneous polymerization deposition, make the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure.
The ESEM front elevation demonstration of the polypyrrole/titanium nitride composite material of coaxial two layers of nano-tube array structure, polypyrrole is optionally deposited on titanium nitride nano pipe outside wall surface, and the pipe thickness of polypyrrole nanotube is 18-30nm, sees Figure of description 5.
The ESEM front elevation of the polypyrrole/titanium nitride/polyaniline composite material of coaxial three layers of nano-tube array structure and side view show, polyaniline selectivity is deposited on titanium nitride nano inside pipe wall face, the pipe thickness of polyaniline nanotube is 5-15nm, sees Figure of description 6.
By the structure of Figure of description 4 known these polypyrrole-titanium nitride-polyaniline composite materials, structural representation is shown in Fig. 1, taking the titanium nitride nano pipe array of pipe wall absolute construction as skeleton, in titanium nitride nano pipe outside wall surface, aggregation deposition forms polypyrrole nanotube, and aggregation deposition forms polyaniline nanotube on titanium nitride nano inside pipe wall face, by titanium nitride nano pipe array 1, the polypyrrole nanotube 2 forming in titanium nitride nano pipe 1 outside wall surface, and the polyaniline nanotube 3 forming on titanium nitride nano pipe 1 internal face, form together the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure.
Structural analysis:
The Raman spectrum test result of the polypyrrole-titanium dioxide-polyaniline composite material of contrast Nano tube array of titanium dioxide, the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure, the polyaniline-composite titania material of coaxial two layers of nano-tube array structure, coaxial three layers of nano-tube array structure shows, there is the characteristic peak of titanium dioxide, polypyrrole, polyaniline in the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure, at 150cm simultaneously
-1, 607cm
-1, 1180cm
-1, 1347cm
-1, 1493cm
-1the obvious characteristic peak occurring corresponds respectively to the stretching vibration of stretching vibration, C-H flexural vibrations, C – N stretching vibration peak, quinone and the semiquinone of the vibration of O-Ti-O angle, phenyl ring, therefore, polypyrrole, polyaniline have been deposited on Nano tube array of titanium dioxide skeleton simultaneously, see Figure of description 7.
The Raman spectrum test result of the polypyrrole-titanium nitride/polyaniline composite material of contrast titanium nitride nano pipe array, the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure, the polyaniline-titanium nitride composite material of coaxial two layers of nano-tube array structure, coaxial three layers of nano-tube array structure shows, there is the characteristic peak of titanium nitride, polypyrrole, polyaniline in the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure, at 210cm simultaneously
-1and 570cm
-1the wide characteristic peak occurring corresponds respectively to titanium nitride crystal TA and TO Raman diaphragm, at 936cm
-1, 1060cm
-1corresponding to the vibration of C-H annular strain, 1380cm
-1, 1509cm
-1, 1599cm
-1the obvious characteristic peak occurring corresponds respectively to C-N stretching vibration, C=N stretching vibration, C=C stretching vibration peak, proves that polypyrrole, polyaniline have been deposited on titanium nitride nano pipe array skeleton simultaneously, see Figure of description 8.
Test chemical property:
(1) the electrochemical capacitor performance of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
Adopt CHI760 electrochemical workstation in three-electrode system, to carry out electrochemical property test, taking the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure as work electrode, platinized platinum is to electrode, and saturated calomel electrode is reference electrode, 0.5mol/L H
2sO
4solution is working electrolyte, and when electrochemistry cyclic voltammetry, sweep speed is 20mV/s, and cyclic voltammetry curve occurs that symmetry redox peak embodies it and goes out good electrochemical reaction invertibity feature, sees Figure of description 9.
With CHI760 electrochemical workstation electro-chemical test cycle charge discharge electrical property, constant current density is 0.5A/g, be respectively 300F/g and 496F/g by the ratio electric capacity that calculates polypyrrole-composite titania material and polypyrrole-titanium dioxide-polyaniline composite material, specific capacitance improves approximately 65%, sees Figure of description 10.
(2) the electrochemical capacitor performance of the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure.
Adopt CHI760 electrochemical workstation in three-electrode system, to carry out electrochemical property test, taking the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure as work electrode, platinized platinum is to electrode, and saturated calomel electrode is reference electrode, 0.5mol/L H
2sO
4solution is working electrolyte, and when electrochemistry cyclic voltammetry, sweep speed is 100mV/s, and cyclic voltammetry curve occurs that symmetry redox peak embodies it and goes out good electrochemical reaction invertibity feature, sees Figure of description 11.
With CHI760 electrochemical workstation electro-chemical test cycle charge discharge electrical property, constant current density is 1.0A/g, be respectively 293.4F/g and 1847F/g by the ratio electric capacity that calculates polypyrrole-titanium dioxide-polyaniline composite material and polypyrrole/titanium nitride/polyaniline composite material, specific capacitance improves approximately 5 times, sees Figure of description 12.
Embodiment 2
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, helps the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprises the following steps:
(1) preparation of Nano tube array of titanium dioxide: titanium sheet is cleaned to 30min, polishing in the hydrogen fluoride/nitric acid/water solution that is 1:4:5 in volume ratio after taking-up in ethanol, acetone, deionized water for ultrasonic successively; Adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as assisting electrode, the aqueous solution taking phosphoric acid, volume fraction 5% methyl alcohol and the volume fraction of the ammonium fluoride of 0.25mol/L, 0.4mol/L as 40% ethylene glycol is as reaction electrolyte solution, under constant voltage 20V condition, react 2h, make the Nano tube array of titanium dioxide of amorphous state; Secondly, the Nano tube array of titanium dioxide of amorphous state is processed in high-temperature calcination, and design temperature is 450 DEG C, and the reaction time is 2h, makes the Nano tube array of titanium dioxide of Anatase;
(2) preparation of the pretreated polypyrrole-composite titania material of chemical polymerization: Nano tube array of titanium dioxide surface uniform is smeared the carbonic allyl ester solution of 1.0mol/L pyrroles and 0.028mol/L ferric trichloride, under 40 DEG C of constant temperature and vacuum condition, process 7min, said process repeats 4 times, makes the pretreated polypyrrole-composite titania material of chemical polymerization.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide of chemical polymerization as work electrode, with 0.2mol/L pyrroles, 0.075mol/L lithium perchlorate, the propene carbonate of volume fraction 4% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.002V/s, the step cycle is 0.2s, scanning hop count is 4, pyrrole monomer optionally forms polypyrrole nanotube in titania nanotube outside wall surface homogeneous polymerization deposition, make the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure.
(4) preparation of the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization: take out and be inverted in hydrothermal reaction kettle after the coaxial two layers of nano-tube array structure polypyrrole-composite titania material composite material that make soak 10min in the acetonitrile solution of 0.1mol/L aniline, 0.05mol/L potassium peroxydisulfate, under 60 DEG C of constant temperature and hydrothermal condition, process 1-2h, make the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization as work electrode, with 0.1mol/L aniline, chloro-2 amino benzoic Acid of 0.4mol/L4-, the dimethyl formamide of volume fraction 7% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.002V/s, the step cycle is 0.5s, scanning hop count is 7, aniline monomer optionally forms polyaniline nanotube in titania nanotube internal face homogeneous polymerization deposition, make the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
Embodiment 3
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, helps the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprises the following steps:
(1) preparation of Nano tube array of titanium dioxide: titanium sheet is cleaned to 30min, polishing in the hydrogen fluoride/nitric acid/water solution that is 1:4:5 in volume ratio after taking-up in ethanol, acetone, deionized water for ultrasonic successively; Adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as assisting electrode, the aqueous solution taking phosphoric acid, volume fraction 6% methyl alcohol and the volume fraction of the ammonium fluoride of 0.15mol/L, 0.5mol/L as 40% ethylene glycol is as reaction electrolyte solution, under constant voltage 30V condition, react 1h, make the Nano tube array of titanium dioxide of amorphous state; Secondly, the Nano tube array of titanium dioxide of amorphous state is processed in high-temperature calcination, and design temperature is 400 DEG C, and the reaction time is 3h, makes the Nano tube array of titanium dioxide of Anatase;
(2) preparation of the pretreated polypyrrole-composite titania material of chemical polymerization: Nano tube array of titanium dioxide surface uniform is smeared the carbonic allyl ester solution of 0.5mol/L pyrroles and 0.025mol/L ferric trichloride, under 35 DEG C of constant temperature and vacuum condition, process 8min, said process repeats 3 times, makes the pretreated polypyrrole-composite titania material of chemical polymerization.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide of chemical polymerization as work electrode, with 0.15mol/L pyrroles, 0.1mol/L lithium perchlorate, the propene carbonate of volume fraction 3% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.004V/s, the step cycle is 0.1s, scanning hop count is 3, pyrrole monomer optionally forms polypyrrole nanotube in titania nanotube outside wall surface homogeneous polymerization deposition, make the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure.
(4) preparation of the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization: take out and be inverted in hydrothermal reaction kettle after the coaxial two layers of nano-tube array structure polypyrrole-composite titania material composite material that make soak 15min in the acetonitrile solution of 0.05mol/L aniline, 0.04mol/L potassium peroxydisulfate, under 55 DEG C of constant temperature and hydrothermal condition, process 2h, make the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization as work electrode, with 0.05mol/L aniline, chloro-2 amino benzoic Acid of 0.5mol/L4-, the dimethyl formamide of volume fraction 5% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.004V/s, the step cycle is 0.8s, scanning hop count is 5, aniline monomer optionally forms polyaniline nanotube in titania nanotube internal face homogeneous polymerization deposition, make the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
Embodiment 4
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, helps the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprises the following steps:
(1) preparation of Nano tube array of titanium dioxide: titanium sheet is cleaned to 30min, polishing in the hydrogen fluoride/nitric acid/water solution that is 1:4:5 in volume ratio after taking-up in ethanol, acetone, deionized water for ultrasonic successively; Adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as assisting electrode, the aqueous solution taking phosphoric acid, volume fraction 8% methyl alcohol and the volume fraction of the ammonium fluoride of 0.3mol/L, 0.4mol/L as 35% ethylene glycol is as reaction electrolyte solution, under constant voltage 20V condition, react 3h, make the Nano tube array of titanium dioxide of amorphous state; Secondly, the Nano tube array of titanium dioxide of amorphous state is processed in high-temperature calcination, and design temperature is 500 DEG C, and the reaction time is 1h, makes the Nano tube array of titanium dioxide of Anatase;
(2) preparation of the pretreated polypyrrole-composite titania material of chemical polymerization: Nano tube array of titanium dioxide surface uniform is smeared the carbonic allyl ester solution of 1.5mol/L pyrroles and 0.030mol/L ferric trichloride, under 45 DEG C of constant temperature and vacuum condition, process 6min, said process repeats 5 times, makes the pretreated polypyrrole-composite titania material of chemical polymerization.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide of chemical polymerization as work electrode, with 0.25mol/L pyrroles, 0.05mol/L lithium perchlorate, the propene carbonate of volume fraction 5% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.001V/s, the step cycle is 0.4s, scanning hop count is 6, pyrrole monomer optionally forms polypyrrole nanotube in titania nanotube outside wall surface homogeneous polymerization deposition, make the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure.
(4) preparation of the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization: take out and be inverted in hydrothermal reaction kettle after the coaxial two layers of nano-tube array structure polypyrrole-composite titania material composite material that make soak 5min in the acetonitrile solution of 0.15mol/L aniline, 0.06mol/L potassium peroxydisulfate, under 65 DEG C of constant temperature and hydrothermal condition, process 1h, make the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization as work electrode, with 0.2mol/L aniline, chloro-2 amino benzoic Acid of 0.3mol/L4-, the dimethyl formamide of volume fraction 10% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.001V/s, the step cycle is 0.2s, scanning hop count is 10, aniline monomer optionally forms polyaniline nanotube in titania nanotube internal face homogeneous polymerization deposition, make the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure.
Embodiment 5
The preparation method of polypyrrole-titanium nitride-polyaniline composite material, helps the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprises the following steps:
(1) preparation of titanium nitride nano pipe array: titanium sheet is cleaned to 30min, polishing in the hydrogen fluoride/nitric acid/water solution that is 1:4:5 in volume ratio after taking-up in ethanol, acetone, deionized water for ultrasonic successively; Adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, titanium sheet is as anode and as work electrode, platinized platinum is as negative electrode and as assisting electrode, the aqueous solution taking phosphoric acid, volume fraction 5% methyl alcohol and the volume fraction of the ammonium fluoride of 0.2mol/L, 0.4mol/L as 40% ethylene glycol is as reaction electrolyte solution, under constant voltage 30V condition, react 2h, make the Nano tube array of titanium dioxide of amorphous state; Secondly, the Nano tube array of titanium dioxide of amorphous state is processed in high-temperature calcination, and design temperature is 450 DEG C, and the reaction time is 2h, makes the Nano tube array of titanium dioxide of Anatase; Then, high-temperature ammonolysis is processed the Nano tube array of titanium dioxide of Anatase, setting ammonia concentration is 99.6%, ammonia flow is 40mL/min, be warming up to 900 DEG C of reaction 1.5h, heating rate is: be 5 DEG C/min from room temperature to 300 DEG C, from 300 to 700 DEG C is 2 DEG C/min, from 700 to 900 DEG C is 1 DEG C/min, makes titanium nitride nano pipe array.
(2) preparation of the pretreated polypyrrole-titanium nitride composite material of chemical polymerization: titanium nitride nano pipe array surface is evenly smeared the carbonic allyl ester solution of 1.0mol/L pyrroles and 0.028mol/L ferric trichloride, under 40 DEG C of constant temperature and vacuum condition, process 7min, said process repeats 4 times, makes the pretreated polypyrrole-titanium nitride composite material of chemical polymerization.
(3) preparation of the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium nitride composite material of chemical polymerization as work electrode, with 0.2mol/L pyrroles, 0.075mol/L lithium perchlorate, the propene carbonate of volume fraction 4% methyl alcohol is that solvent forms reaction electrolyte solution, electrochemical polymerization reaction adopts step scanning voltammetry, it is 0.55V that take-off potential is set, termination current potential is 1.1V, current potential increment is 0.002V/s, the step cycle is 0.2s, scanning hop count is 5, pyrrole monomer optionally forms polypyrrole nanotube in titanium nitride nano pipe outside wall surface homogeneous polymerization deposition, make the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure.
(4) preparation of the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization: take out and be inverted in hydrothermal reaction kettle after the coaxial two layers of nano-tube array structure polypyrrole-titanium nitride composite material that make soak 10min in the acetonitrile solution of 0.1mol/L aniline, 0.05mol/L potassium peroxydisulfate, under 60 DEG C of constant temperature and hydrothermal condition, process 1.5h, make the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization.
(5) preparation of the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization as work electrode, with 0.01mol/L aniline, chloro-2 amino benzoic Acid of 0.4mol/L4-, the dimethyl formamide of volume fraction 7% forms reaction electrolyte solution, under 1000W xenon lamp irradiates, light helps electrochemical polymerization reaction to adopt step scanning voltammetry, take-off potential is set is-0.2V, termination current potential is 1.0V, current potential increment is 0.002V/s, the step cycle is 0.6s, scanning hop count is 7, aniline monomer optionally forms polyaniline nanotube in titanium nitride nano inside pipe wall face homogeneous polymerization deposition, make the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure.
Embodiment 6
Substantially the same manner as Example 5, difference is only: high-temperature ammonolysis is processed Nano tube array of titanium dioxide, and setting ammonia concentration is 99.0%, and ammonia flow is 30mL/min, is warming up to 900 DEG C of reaction 2h.
Embodiment 7
Substantially the same manner as Example 5, difference is only: high-temperature ammonolysis is processed Nano tube array of titanium dioxide, and setting ammonia concentration is 99.4%, and ammonia flow is 50mL/min, is warming up to 900 DEG C of reaction 1h.
Claims (10)
1. the coaxial three layers of nanotube array composite material of polypyrrole-titanium dioxide or titanium nitride-polyaniline, is characterized in that: the polypyrrole nanotube (2) that comprise the titanium dioxide of pipe wall absolute construction or titanium nitride nano pipe array skeleton (1), forms at titanium dioxide or titanium nitride nano pipe array skeleton (1) outside wall surface aggregation deposition and the polyaniline nanotube (3) forming at titanium dioxide or titanium nitride nano pipe array skeleton (1) internal face aggregation deposition; The coaxial three layers of nanotube array composite material of described polypyrrole-titanium dioxide or titanium nitride-polyaniline are one group of array structure with the tight ordered arrangement formation of three layers of nanotube of concentric shafts, described three layers of nanotube with concentric shafts are outer is polypyrrole nanotube, intermediate layer is titanium dioxide or titanium nitride nano pipe, and internal layer is polyaniline nanotube.
2. the coaxial three layers of nanotube array composite material of a kind of polypyrrole-titanium dioxide according to claim 1 or titanium nitride-polyaniline, it is characterized in that: the pipe thickness of titanium dioxide or titanium nitride nano pipe is that 10-20nm, internal diameter are that 80-130nm, length are 860-960nm, and between adjacent titanium dioxide or titanium nitride nano pipe, distance is 30-68nm; In the time that skeleton is Nano tube array of titanium dioxide, the pipe thickness of polypyrrole nanotube is 8-15nm, and the pipe thickness of polyaniline nanotube is 8-11nm; In the time that skeleton is titanium nitride nano pipe array, the pipe thickness of polypyrrole nanotube is 18-30nm, and the pipe thickness of polyaniline nanotube is 5-15nm.
3. the preparation method of a kind of polypyrrole-titanium dioxide described in claim 1 to 2 any one or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: help the synthetic reaction method of substep selectivity of electrochemical polymerization reaction to be prepared from by chemical polymerization, electrochemical polymerization reaction and light, comprise the following steps:
(1) preparation of Nano tube array of titanium dioxide: adopt constant potential anodic oxidation synthetic method, in two electrode chemical reaction systems, using titanium sheet as anode and as work electrode, using platinized platinum as negative electrode and as assisting electrode, using the mixed aqueous solution of ammonium fluoride, phosphoric acid, methyl alcohol and ethylene glycol as reaction electrolyte solution, under constant voltage 20-30V condition, react 1-3h, make the Nano tube array of titanium dioxide of amorphous state; The Nano tube array of titanium dioxide of amorphous state, at 400-500 DEG C of high-temperature calcination 1-3h, is made to the Nano tube array of titanium dioxide of Anatase;
(2) preparation of titanium nitride nano pipe array: step (1) makes the Nano tube array of titanium dioxide of Anatase under pure ammonia atmosphere condition, and 900 DEG C of constant temperature nitrogen treatment 1-2h, make titanium nitride nano pipe array;
(3) preparation of the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization: the titanium nitride nano pipe array surface that the Nano tube array of titanium dioxide that step (1) is made or step (2) make is evenly smeared the carbonic allyl ester solution of pyrroles and ferric trichloride, under vacuum condition, 35-45 DEG C of constant temperature is processed 6-8min, repeat 3-5 time, obtain the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization;
(4) preparation of polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material: in three-electrode electro Chemical reaction system, taking the pretreated polypyrrole-titanium dioxide of chemical polymerization or the pretreated polypyrrole-titanium nitride composite material of chemical polymerization as work electrode, using the propene carbonate mixed solution of pyrroles, lithium perchlorate and methyl alcohol as reaction electrolyte solution, adopt step scanning voltammetry electrochemical polymerization reaction to make polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material;
(5) preparation of the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization: polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material that step (4) is made soak after 5-15min in the acetonitrile solution of aniline, potassium peroxydisulfate, be inverted in hydrothermal reaction kettle, 55-65 DEG C of incubation water heating processed 1-2h, makes the pretreated polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization;
(6) preparation of coaxial three layers of nanotube array composite material: in three-electrode electro Chemical reaction system, pretreated polypyrrole-titanium dioxide-the polyaniline composite material of chemical polymerization making taking step (5) or the pretreated polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization are as work electrode, using aniline, chloro-2 amino benzoic Acid of 4-and the dimethyl formamide aqueous solution as reaction electrolyte solution, under 1000W xenon lamp irradiates, adopt step scanning voltammetry light to help electrochemical polymerization reaction to make coaxial three layers of nanotube array composite material.
4. the preparation method of a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: in step (1), in reaction electrolyte solution, the molar concentration of ammonium fluoride is that the molar concentration of 0.15-0.30mol/L, phosphoric acid is 0.4-0.5mol/L, and the volume fraction of methyl alcohol is that the volume fraction of 5-8%, ethylene glycol is 35-45%; Preferably, the molar concentration of ammonium fluoride is that the molar concentration of 0.2mol/L, phosphoric acid is that the volume fraction of 0.5mol/L, methyl alcohol is 5%, the volume fraction of ethylene glycol is 40%.
5. the preparation method of a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: in step (2), pure ammonia atmosphere environment is: ammonia concentration is 99.0-99.6%, and ammonia flow is 30-50mL/min; 900 DEG C of constant temperature nitrogen treatment programs are: be warming up to 900 DEG C of constant temperature and process 1-2h; Heating schedule is: be 5 DEG C/min from room temperature to 300 DEG C, from 300 to 700 DEG C is 2 DEG C/min, and from 700 to 900 DEG C is 1 DEG C/min.
6. the preparation method of a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: in step (3), in the carbonic allyl ester solution of pyrroles and ferric trichloride, pyrroles's molar concentration is 0.5-1.5mol/L, preferably 1.0mol/L, the molar concentration of ferric trichloride is 0.025-0.030mol/L, preferably 0.028mol/L.
7. the preparation method of a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: in step (4), in the propene carbonate mixed solution of pyrroles, lithium perchlorate and methyl alcohol, pyrroles's molar concentration is 0.15-0.25mol/L, the molar concentration of lithium perchlorate is 0.05-0.1mol/L, the volume fraction 3-5% of methyl alcohol; Preferably, pyrroles's molar concentration is 0.2mol/L, and the molar concentration of lithium perchlorate is 0.075mol/L, the volume fraction 4% of methyl alcohol; Step scanning voltammetry condition is: take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is 0.001-0.004V/s, and the step cycle is 0.1-0.4s, and scanning hop count is 3-6.
8. the preparation method of a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, it is characterized in that: in step (5), in the acetonitrile solution of aniline, potassium peroxydisulfate, the molar concentration of aniline is that the molar concentration of 0.05-0.15mol/L, potassium peroxydisulfate is 0.04-0.06mol/L, preferably, the molar concentration of aniline is that the molar concentration of 0.10mol/L, potassium peroxydisulfate is 0.05mol/L.
9. the preparation method of a kind of coaxial three layers of nanotube array composite material according to claim 3, it is characterized in that: in step (6), in aniline, the chloro-amino benzoic Acid of 4-and the dimethyl formamide aqueous solution, the molar concentration of aniline is that the molar concentration of chloro-2 amino benzoic Acid of 0.05-0.2mol/L, 4-is that the volume fraction of 0.3-0.5mol/L, dimethyl formamide is 5-10%; Step scanning voltammetry condition is: take-off potential is-0.2V, and termination current potential is 1.0V, and current potential increment is 0.001-0.004V/s, and the step cycle is 0.2-0.8s, and scanning hop count is 5-10.
10. the application in the coaxial three layers of nanotube array composite material electrochemical energy storage field of a kind of polypyrrole-titanium dioxide described in claim 1-2 any one or titanium nitride-polyaniline.
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