CN103165283B - A kind of enhancing TiO2The method of electrode electro Chemical performance - Google Patents
A kind of enhancing TiO2The method of electrode electro Chemical performance Download PDFInfo
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- CN103165283B CN103165283B CN201310095453.2A CN201310095453A CN103165283B CN 103165283 B CN103165283 B CN 103165283B CN 201310095453 A CN201310095453 A CN 201310095453A CN 103165283 B CN103165283 B CN 103165283B
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Abstract
The invention discloses a kind of easy, strengthen TiO inexpensively, efficiently2The method of electrode electro Chemical performance, namely to TiO2Electrode carries out reverse making alive process.At the TiO with annealing2Electrode is negative electrode, and carbon-point is in two electrode systems of anode, with neutrality, acidity or alkaline solution for electrolyte, is electrochemically reacted process.This method is without special installation, by H in electric field driven solution+Ion, directly at TiO2Electrode introduces doping and defect, strengthens TiO2The chemical property of electrode, reduces TiO simultaneously2Energy gap increases absorptivity and improves electrode conductivity.The inventive method will not destroy TiO2Original structure (such as TiO2Nanotube, nano-wire array), make TiO2Electrode can be preferably applied for energy storage field, photocatalysis, solaode, the field such as photochromic.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of easy, strengthen TiO inexpensively, efficiently2The method of electrode electro Chemical performance.The method can strengthen TiO2As the performance of energy storage device electrode, electrode of solar battery and photoelectrocatalysimaterial material, it is applied to other field at the same time as good conductive material.
Background technology
Along with global IT application and industrialized fast development, various computers, miniature electronic apparatus and mobile communication equipment become increasingly popular, in the urgent need to high performance memory ready power supply.On the other hand, the consumption of fuel-engined vehicle causes energy shortage and serious environmental pollution, and this promotes people to design production low energy consumption and low emission electric automobile or mixed power electric car.But at present conventional secondary cell is not enough due to power density, it is impossible to meet alone the power demand of electric automobile, it is necessary to the ultracapacitor of high power density with the use of.Meanwhile, people are seeking new clear energy sources and the method alleviating environmental pollution always, such as H2Big energy is released in energy burning and product is water, and water can reuse again generation H2, whole cyclic process does not have any pollution.But it is how easy and prepare H at a low price2It is difficult to solve always.TiO2Owing to having semiconductor property and the advantage such as stable chemical nature, with low cost, environmental protection, it is not only a kind of super capacitance electrode material that can be used for electrochemical energy storing device, and be a kind of rising photoelectrocatalysimaterial material, can be applicable to photoelectrocatalysis decomposition water and prepare H2With the Organic substance that degraded causes environmental pollution.Therefore, TiO2As the electrode material of energy storage device, solaode or photoelectro catalytic system, no matter become in global range is the study hotspot of academia or industrial circle.
But, as the TiO directly using eigenstate2During as energy storage device electrode or photochemical catalyst electrode, its chemical property is poor.Such as, TiO2When nano-particle prepares into super capacitor electrode, only presenting relatively low electric double layer capacitance, capacity is 10-40 μ F/cm2, this is mainly by eigenstate TiO2Low conductance property caused by.Additionally, TiO2When nano-particle is used as photoelectrocatalysielectrode electrode, its efficiency of light absorption is less than 3%, and catalytic efficiency is low.This again with TiO2Energy gap wider (3.2eV), only has response and Carrier recombination is too fast etc. that factor is relevant ultraviolet light.
Visible, improve TiO2Electrical conductivity be strengthen it as the key of energy storage device electrode performance.In order to improve TiO2Electrical conductivity and chemical property, currently mainly adopt and introduce metal (ZKZheng, etal.JournalofMaterialsChemistry21 (2011) 9079) or the method for nonmetallic inclusion (XChen, etal.ChemicalReviews107 (2007) 2891) at TiO2Energy gap produces state acceptor or donor, thus reducing energy gap to reach to improve the purpose of electrical conductivity.But, the instability problem of the such as Carrier recombination and thermal and electrochemical that cause due to the introducing of adulterant is still difficult to solve (RAsahi, etal.Science293 (2001) 269).On the other hand, by TiO2Lattice introduces Lacking oxygen (Ti3+Position) produce donor state auto-dope also can regulate and control its band structure, this auto-dope method can be greatly enhanced TiO2To the response of visible ray to infrared light, its electrical conductivity and electro-chemical activity.But, maximally effective auto-dope method is all at high temperature carry out (XHLu, etal.NanoLetters12 (2012) 1690 so far;XDJiang, etal.JournalofPhysicalChemistryC116 (2012) 22619) or need long processing procedure (XBChen, etal.Science331 (2011) 746).Therefore, a kind of method easy, cheap, efficient is found to strengthen TiO2Chemical property is the key of solution problem.
Summary of the invention
It is an object of the invention to provide a kind of easy, strengthen TiO inexpensively, efficiently2The method of electrode electro Chemical performance, makes TiO2Electrode material can meet the application requirement in energy storage device, photoelectrocatalysis, solaode, the field such as photochromic.
The technical solution realizing the object of the invention is: a kind of easy, strengthen TiO inexpensively, efficiently2The method of electrode electro Chemical performance, to prepared TiO2Electrode carries out reverse making alive process: namely with the TiO of crystalline state2Electrode is negative electrode, and carbon-point is in two electrode systems of anode, and concentration of electrolyte is 0.1-2M, is electrochemically reacted process under room temperature, and between two electrodes, spacing is 0.5-10cm, applies voltage and be 2-10V and reacting treatment time is 5-360s.
Described electrolyte is neutral, acid or alkaline solution, it is preferable that sodium salt, potassium salt, ammonium salt, hydrochloric acid, sulphuric acid, phosphoric acid, sodium hydroxide or potassium hydroxide solution.
Preparation TiO of the present invention2The method of electrode can adopt anodizing, hydro-thermal method, template, sol-gal process, microemulsion method and vapour deposition process etc., and wherein anodizing can adopt constant voltage oxidizing process and pulse oxidizes method.
Compared with prior art, the present invention have the prominent advantages that processing method is simple and easy to do, it is not necessary to special installation: prepare TiO with anodizing2Time anode contrary, only need to by TiO2Changing negative electrode into, namely reversely namely making alive process certain time is remarkably improved TiO2Electrode electro Chemical performance.Due to H in electric field driven solution+Ion, directly at TiO2Electrode introduces doping and defect, greatly reduces TiO2Energy gap so that it is chemical property and PhotoelectrocatalytiPerformance Performance and electrical conductivity are improved significantly.This processing method will not destroy TiO2Original structure (such as TiO2Nanotube, nano-wire array), make TiO2Electrode can be preferably applied for energy storage field and photoelectrocatalysis field to solve energy problem and problem of environmental pollution, simultaneously TiO2Electrode also can be applied to other field as good conductive material.
Accompanying drawing explanation
Fig. 1 is the untreated TiO of embodiment 1 preparation2The cyclic voltammetry curve of electrode.
Fig. 2 is the TiO that embodiment 1 processes through reverse making alive2The cyclic voltammetry curve of electrode.
Fig. 3 is the untreated TiO of embodiment 1 preparation2The AC impedance curve of electrode.
Fig. 4 is the TiO that embodiment 1 processes through reverse making alive2The AC impedance curve of electrode.
Fig. 5 is the untreated TiO of embodiment 1 preparation2The light-catalysed photocurrent curve of electrode.
Fig. 6 is the TiO that embodiment 1 processes through reverse making alive2The light-catalysed photocurrent curve of electrode.
Detailed description of the invention
Further illustrate the present invention by the examples below.
Embodiment 1
Constant voltage oxidizing process is adopted to prepare TiO2Electrode: with titanium foil for working electrode, carbon-point is carry out anodic oxidation in two electrode systems to electrode, and electrolyte is 0.5wt%NH4F and 2vol%H2The ethylene glycol solution of O.First, by titanium foil in atmosphere 450°C anneals 20min, to eliminate structural stress, then uses acetone, second alcohol and water ultrasonic cleaning titanium foil 10min successively.Anodic oxidation carries out 2h with constant voltage 60V, and then ultrasonic 30min removes oxide-film, again cleans successively with acetone, second alcohol and water and stays dimpled titanium foil.Carrying out two-step anodization again, oxidizing condition is identical with once oxidation, and oxidation takes out TiO after terminating2Electrode deionized water is rinsed well, dries.The amorphous state TiO prepared2Electrode is ordered nano-tube array structure, and tube diameters is 40-60nm, and thickness is about 12 μm.By prepare with the TiO at the bottom of titanio2Electrode puts into tube annealing crystallization, annealing temperature 450°C.Then, reverse making alive, namely with the crystalline state TiO of annealing2Electrode is negative electrode, and carbon-point is two electrode systems of anode, is 0.5MNa at electrolyte2SO4Neutral solution in be electrochemically reacted, two electrode spacing 2.5cm, voltage 5V and response time 30s.
Fig. 1 and Fig. 2 is TiO that is untreated and that process2Electrode sweeps speed cyclic voltammetric (CV) curve for 100mV/s, as seen from the figure, and the TiO of process2Electrode has obvious current-responsive at positive potential, and the area that CV curve surrounds substantially increases.Fig. 3 and Fig. 4 is TiO that is untreated and that process2Electrode, at amplitude 10mV, tests frequency ac impedance spectroscopy (EIS) from 100kHz to 0.1Hz.The TiO processed2In electrode EIS curve, semicircle radius is only small, it is meant that only small electrode internal resistance and higher electrode conductivity.With 2MLi2SO4Electrolyte, 0.05mA/cm2Electric current density carries out charge-discharge test, and voltage range-0.3-0.6V(Ag/AgCl is reference electrode), untreated TiO2Electrode discharge is 0.98mF/cm than electric capacity2；And the TiO processed2Electrode reaches 18.5mF/cm than electric capacity2.Fig. 5 and Fig. 6 is TiO that is untreated and that process2The light-catalysed photoelectricity flow graph of electrode.Under the sunlight being 1.5G with AM under the ultraviolet light (UV) of wavelength 365nm, untreated TiO2Electrode photoelectric stream respectively may be about 85 μ A and 106 μ A, and the photoelectric current of process can reach about 213 μ A and 225 μ A respectively.
Embodiment 2
Hydro-thermal method is adopted to prepare TiO2Electrode: under room temperature, isopropyl titanate and isopropanol are joined according to volume ratio 1:1 in the acetic acid of pH=2 and be mixed and stirred for, then 80°C oil bath is heated about lh and is stirred vigorously, after solution is moved in autoclave, 250 after sealing°12h is placed under C.Last ultrasonic disperse colloid solution, 120°C heats certain time, obtains opalescent colloidal, is applied on the electro-conductive glass cleaned up, and coated area is 1.2cm2, dry.Reverse making alive technique is with embodiment 1.Test result shows, hydro-thermal method prepares TiO2The ratio electric capacity of electrode is 63 μ F/cm2；TiO after process2Electrode reaches 1.06mF/cm than electric capacity2.Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, hydro-thermal method prepares TiO2The photoelectric current of electrode respectively may be about 15 μ A and 28 μ A；Photoelectric current after process can reach about 46 μ A and 59 μ A respectively.
Embodiment 3
Adopt template synthesis TiO2Electrode: the Woelm Alumina that template is with aluminium substrate (removes barrier layer, aperture 60nm, thickness 20 microns, area 1.2cm2), adopt 0.1M (NH4)2TiF6For presoma.Woelm Alumina with aluminium substrate is immersed in precursor solution, takes out after reaction 1h, rinse well with deionized water, dry.Reverse making alive technique is with embodiment 1.Test result shows, the TiO after process2Electrode is 5.89mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 136 μ A and 163 μ A respectively.
Embodiment 4
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.Electrolyte used by reverse making alive technique is 2MNa2SO4Neutral solution, other reverse making alive condition and embodiment 1 are identical.Test result shows, the TiO after process2Electrode is 20.8mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 224 μ A and 256 μ A respectively.
Embodiment 5
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.The acid solution that electrolyte is 0.1MHCl used by reverse making alive technique, other reverse making alive condition is identical with embodiment 1.Test result shows, the TiO after process2Electrode is 15.7mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 185 μ A and 212 μ A respectively.
Embodiment 6
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.The alkaline solution that electrolyte is 1MKOH used by reverse making alive technique, other reverse making alive condition is identical with embodiment 1.Test result shows, the TiO after process2Electrode is 18.94mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 197 μ A and 208 μ A respectively.
Embodiment 7
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.Two electrode spacings in reverse making alive process are 0.5cm, and applying voltage is 2V, and other reverse making alive process conditions are identical with embodiment 1.Test result shows, the TiO after process2Electrode is 4.3mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 124 μ A and 147 μ A respectively.
Embodiment 8
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.Two electrode spacings in reverse making alive process are 10cm, and the response time is 360s, and other reverse making alive process conditions are identical with embodiment 1.Test result shows, the TiO after process2Electrode is 12.8mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 164 μ A and 183 μ A respectively.
Embodiment 9
Constant voltage oxidizing process prepares TiO2Electrode is identical with embodiment 1.Annealing condition is with embodiment 1.Voltage in reverse making alive process is 10V, and the response time is 5s, and other reverse making alive process conditions are identical with embodiment 1.Test result shows, the TiO after process2Electrode is 9.63mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 152 μ A and 182 μ A respectively.
Embodiment 10
Pulse oxidizes method prepares TiO2The electrolyte of electrode is consistent with embodiment 1 with the pretreating process of titanium foil.Oxidizing process, imposes 60V voltage, often stops 10s after oxidation 10s, and total time is 4h.Annealing and reverse making alive technique are with embodiment 1.Test result shows, the TiO after process2Electrode is 23.5mF/cm than electric capacity2；Under the UV of wavelength 365nm and under the sunlight that AM is 1.5G, its photoelectric current can reach about 239 μ A and 251 μ A respectively.
Claims (5)
1. one kind strengthens TiO2The method of electrode electro Chemical performance, it is characterised in that to TiO2Electrode carries out reverse making alive process: namely at the TiO with crystalline state2Electrode is negative electrode, and carbon-point is in two electrode systems of anode, and concentration of electrolyte is 0.1-2M, is electrochemically reacted process under room temperature, and between two electrodes, spacing is 0.5-10cm, applies voltage and be 2-10V and reacting treatment time is 5-360s.
2. enhancing TiO according to claim 12The method of electrode electro Chemical performance, it is characterised in that described electrolyte is neutral, acid or alkaline solution.
3. enhancing TiO according to claim 22The method of electrode electro Chemical performance, it is characterised in that described electrolyte particular certain cancers, potassium salt, ammonium salt, hydrochloric acid, sulphuric acid, phosphoric acid, sodium hydroxide or potassium hydroxide solution.
4. enhancing TiO according to claim 12The method of electrode electro Chemical performance, it is characterised in that described TiO2Electrode adopts anodizing, hydro-thermal method, template, sol-gal process, microemulsion method or vapour deposition process to prepare.
5. enhancing TiO according to claim 42The method of electrode electro Chemical performance, it is characterised in that described anodizing comprises constant voltage oxidizing process or pulse oxidizes method.
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| CN103590087B (en) * | 2013-10-16 | 2016-03-16 | 中国科学院合肥物质科学研究院 | Internal orifice dimension mechanical periodicity and cycle adjustable TiO 2nano-pipe array thin film and preparation method thereof |
| CN103680978B (en) * | 2013-12-20 | 2017-04-19 | 南京理工大学 | High-specific-volume low-voltage aluminum electrolytic capacitor and manufacturing method thereof |
| CN103924279B (en) * | 2014-04-10 | 2016-08-24 | 北京工业大学 | A kind of pulse anodic oxidation prepares method prepared by high-sequential titanium dioxide nano-pipe array thin film |
| CN105448539B (en) * | 2014-08-20 | 2017-11-14 | 南京理工大学 | One kind improves TiO2The method of electrode capacitance |
| CN104658768B (en) * | 2014-12-11 | 2017-12-22 | 湖北大学 | The preparation method and its ultracapacitor of titanium oxide |
| CN108648927B (en) * | 2018-04-28 | 2020-02-14 | 南京理工大学 | Titanium oxide nanotube-based supercapacitor electrode and preparation method thereof |
| CN110344097B (en) * | 2019-07-26 | 2021-04-27 | 南京理工大学 | Method for preparing anodic titanium oxide nanoflower electrode |
| CN113774426B (en) * | 2021-10-20 | 2023-03-10 | 中国科学技术大学 | Electrocatalyst and preparation method thereof |
| CN114427112A (en) * | 2022-01-27 | 2022-05-03 | 中国人民解放军陆军工程大学 | Method for preparing multi-color photochromic Ag/TiO2 film |
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