CN102280269A - TiO2 nanotube array photoanode and preparation method thereof - Google Patents

TiO2 nanotube array photoanode and preparation method thereof Download PDF

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CN102280269A
CN102280269A CN2011101900174A CN201110190017A CN102280269A CN 102280269 A CN102280269 A CN 102280269A CN 2011101900174 A CN2011101900174 A CN 2011101900174A CN 201110190017 A CN201110190017 A CN 201110190017A CN 102280269 A CN102280269 A CN 102280269A
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tube array
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陈福义
樊莉红
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Northwestern Polytechnical University
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Abstract

The invention provides a TiO2 nanotube array photoanode and a preparation method thereof. The photoanode is characterized by electrodepositing a silver film on the surface of the TiO2 nanotube array of the photoanode, wherein the microscopic surface topography of the silver film is randomly distributed dendrites; the primary dendrites are 6-15mu m long; the secondary dendrites are 600nm-3mu m long; and the space between the secondary dendrites is 100-300nm. The silver modified TiO2 nanotube array photoanode is obtained by reasonably controlling the concentration, electrodeposition temperature, deposition potential and deposition time of the silver nitrate electrolyte. The silver is used as the noble metal instead of gold and electrodeposition is used instead of the electron beam lithography technology to prepare the silver nanoparticle-TiO2 nanotube array structure as the solar cell photoanode, thus lowering the cost and shortening the preparation period. The short-circuit current density and open-circuit voltage of the silver nanoparticle-TiO2 nanotube array photoanode after being modified by the metal are greatly improved compared with the short-circuit current density and open-circuit voltage of the silver nanoparticle-TiO2 nanotube array photoanode before being modified by the metal.

Description

A kind of TiO＜sub〉2＜/sub〉nanotube array photo-anode and preparation method thereof
Technical field
The present invention relates to area of solar cell, specifically is a kind of solar battery light anode and preparation method thereof.
Background technology
In recent years, dye sensitized nano crystal salar battery (DSSC) is since invention, and, technology low with cost simply reaches the advantage of stable performance, becomes both at home and abroad the competitively focus of research.In order to improve the electricity conversion of battery, the researcher updates sensitizer, electrolyte and the semiconductor optical anode material of battery.Wherein, selecting suitable semiconductor optical anode material is the electricity conversion important channel of improving battery.From the eighties, the research group of the Gratzel of Lausanne, SUI higher technical school just is devoted to dye sensitization TiO 2The research of thin-film solar cells, " A Low-cost, the High-efficiency Solar-cell Based on Dye-sensitized Colloidal TiO that on Nature (1991,353:737～740), deliver 2Films ", indicate with porous TiO 2The research of film light anode has obtained breakthrough finally.From then on TiO 2The light anode material has caused people's attention gradually.But because TiO 2There is the bottleneck that can't break through in semiconductor self, and as greater band gap (3.2eV) etc., this has reduced the electricity conversion of DSSC to a certain extent, has restricted the process of industrialization of DSSC, so, TiO 2The modification of light anode becomes one of main path that improves the DSSC performance.
At present, for dye sensitized nano crystal salar battery TiO 2The study on the modification of light anode has been obtained certain achievement.Method of modifying commonly used mainly contains two kinds: one is to use TiO 2Nanotube replaces TiO 2Nano particle, for example, calendar year 2001, people such as U.S. scientist Grimes just J.Mater.Res (2001, utilize electrochemistry anodic oxidation successfully to prepare TiO in the paper of 16:3331-3335) delivering " Titanium Oxide Nanotube Prepared by Anodic Oxidation " 2Nano-tube array.Experimental results demonstrate, compare TiO 2Nano particle, TiO 2Nano-tube array has better electric transmission character.Another method is noble metal decorated, for example, Japan scholar Nishijima etc. are at J.Phys.Chem.Lett (2010,1,2031-2036) disclosed document " Plasmon-Assisted Photocurrent Generation from Visible to Near-Infrared Wavelength Using a Au-Nanorods/TiO 2Electrode " in, propose at TiO 2Single-crystal surface deposition Au nanometer stick array is found Au-TiO 2Structure can have photovoltaic performance in visible light-near infrared range.
In the method for modifying of dye-sensitized solar cell anode, use TiO 2Nanotube replaces TiO 2Nano particle can effectively improve TiO 2Intercrystalline connectedness is eliminated the charge carrier complex centre, improves the efficiency of transmission of electronics, thereby reduces photoelectronic loss.But as dye-sensitized solar cell anode, simple TiO 2Nanotube still can't fundamentally solve TiO 2Problems such as the optical semiconductor response region is little, and collection efficiency is low.
The Au-TiO of people such as Nishijima preparation 2What structure adopted is exactly noble metal decorated method, but this use electron beam lithography is realized the method that metal is modified very significant disadvantages is arranged.At first, though electron beam lithography machining accuracy height must under vacuum condition, carry out, the processing cost costliness, equipment drops into high, belongs to experimental study equipment, but will be applied to photovoltaic technology, can bring huge cost pressure; Add photoetching technique length consuming time, complex process can not large-scale industrial production, so this method is difficult to use in solar cell industry is produced.
In sum; existing noble metal decorated technology can not be used for the large-scale low-cost suitability for industrialized production; need a kind of new technology of invention to solve cost height in the present noble metal decorated smooth anode preparation technology; the problem that manufacturing cycle is long; and further promote the green low cost of DSSC technology to develop, alleviate the problem of energy crisis that the world today faces.
Publication number be CN101271774A patent in, Tongji University discloses a kind of material, its preparation method and application that can be used for solar battery light anode.This smooth anode uses electrochemical production gold, silver, platinum, palladium nanometer rods, nanosphere to make the metal surface plasma medium, adopts the TiO of gel process preparation 2Film is made electronic transmission medium, with FeCl 2/ FeCl 3Ethylene glycol-lithium nitrate solution make electrolyte.Although this patent and the application's patent mechanism basically identical, existing patent exists significant disadvantages: at first, adopt the TiO of gel process preparation 2Film compares TiO 2The electric transmission character of nano-tube array is poor; Secondly, use rare precious metal platinum as the surface plasma medium, yield poorly and the cost height, it is extensive not meet solar cell, cheaply development trend.
Summary of the invention
For overcome exist in the prior art or the cost height, length consuming time, light collection efficiency is low to be waited not enoughly, the present invention proposes a kind of TiO 2Nanotube array photo-anode and preparation method thereof.
The TiO that the present invention proposes 2The TiO of nanotube array photo-anode 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
The invention allows for a kind of preparation TiO 2The method of nanotube array photo-anode, its concrete preparation process is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut slivering, polishing, with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively, ultrasonic power is 200 watts.
Step 2, preparation electrolyte: electrolyte is ammonium fluoride electrolyte or hydrogen fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte.Wherein:
Ammonium fluoride electrolyte is made up of the ammonium fluoride of 0.25wt%, the deionized water of 2.5vol% and the ethylene glycol of 97.5vol%; Load weighted ammonium fluoride is placed beaker and adds deionized water, be stirred to ammonium fluoride and dissolve fully; Add ethylene glycol in being dissolved with the aqueous solution of ammonium fluoride, fully stirring mixes the aqueous solution of ammonium fluoride and ethylene glycol, obtains the mixed solution of ammonium fluoride and ethylene glycol; Use 2.0molL -1Sulfuric acid solution the mixed solution pH value of ammonium fluoride and ethylene glycol is transferred to 6, obtain ammonium fluoride electrolyte;
Hydrogen fluoride electrolyte is by 0.1molL -1Hydrogen fluoride and 2.0molL -1The mixed solution formed of sulfuric acid.Load weighted hydrogen fluoride is placed beaker and adds deionized water, be stirred well to hydrogen fluoride and deionized water mixes fully; Add sulfuric acid in being dissolved with the hydrofluoric aqueous solution, fully stirring mixes the hydrofluoric aqueous solution and sulfuric acid, obtains hydrogen fluoride electrolyte;
Silver nitrate electrolyte is by 0.05～1.0molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte;
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte.
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of DC power supply is connected titanium foil, and negative pole connects platinum guaze; Ammonium fluoride electrolyte or hydrogen fluoride electrolyte are imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under ammonium fluoride electrolyte or the hydrogen fluoride liquid level of electrolyte, platinum guaze is immersed in the described electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm; The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 17～30 ℃; Use ammonium fluoride electrolyte at titanium foil surface preparation TiO 2During nano-tube array, oxidation voltage is 30V, and oxidization time is 4h; Use hydrogen fluoride electrolyte at titanium foil surface preparation TiO 2During nano-tube array, oxidation voltage is 20V, and oxidization time is 1h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array.
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed.
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2Between nano-tube array and the platinum guaze at a distance of 2cm; Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 17 ℃～30 ℃, sedimentation potential is-0.4～-1.1VSCE, sedimentation time is 1～5min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
The present invention has integrated existing TiO 2Nanotube and noble metal decorated two kinds of methods use silver to replace gold to make noble metal, use electro-deposition to replace electron beam lithography to prepare Nano silver grain-TiO 2Nano-tube array structure is as solar battery light anode.Compare electron beam lithography, use the electrodeposition technology for preparing metal to modify the light anode, reduced cost, shortened manufacturing cycle.The present invention uses linear sweep voltammetry and AC impedence method that prepared light anode is measured.Obtained current-voltage curve and the electrochemical impedance spectroscopy of light anode under simulated solar illumination.The performance parameter of two kinds of light anodes sees the following form.Observe modified by silver TiO 2The photovoltaic character that nanotube array photo-anode is compared before modifying is found, the Nano silver grain-TiO after modifying through metal 2Short-circuit current density and open circuit voltage all improved a lot before nanotube array photo-anode was compared and modified.Short-circuit current density and open circuit voltage are high more, show that its light collection efficiency and electron injection efficiency are high more.
Subordinate list: the photovoltaic performance parameter of used for solar batteries modified by silver light anode
Figure BSA00000533293500041
Modified by silver TiO 2The reaction mechanism that nanotube array photo-anode improves electricity conversion is: photoelectronic generation approach on the light anode has been widened in the modification of Nano silver grain effectively, mainly contain two aspects, the one, the phototransformation that Nano silver grain absorbs is a surface plasma, and this excite state electronics is injected into TiO 2Conduction band has increased the light collection efficiency of light anode; The 2nd, Nano silver grain edge electric field space and The limited time have improved near field intensity, have promoted the electron excitation of Nano silver grain at visible light wave range, have improved the injection efficiency of electronics.In addition, the part silver particles enters into TiO 2In the nanotube, make TiO 2The local good electron conducting shell that forms of matrix makes and injects electronics at TiO 2In migration become and be more prone to, thereby reduced photoelectron-hole to compound, reduced loss of electrons.
The present invention is comprehensively existing method of modifying, adopts low cost process to realize the noble metal modified by silver, preparation Nano silver grain-TiO 2The dye-sensitized solar cell anode of nano-tube array structure.The present invention can reduce in the prior art the undue dependence to expensive noble metal, and further improves the photovoltaic performance of DSSC, makes solar energy obtain to a greater degree utilizing, and finally reaches the purpose of alleviating energy pressure.
Description of drawings
Accompanying drawing 1 is modified by silver TiO 2The preparation flow figure of nanotube array photo-anode;
Accompanying drawing 2 is modified by silver TiO 2The X-ray diffractogram of nanotube array photo-anode;
Accompanying drawing 3 is TiO 2Current density-voltage curve under nano-tube array and the two kinds of anode simulated solar irradiations of not sharing the same light;
Accompanying drawing 4 is TiO 2Nano-tube array and two kinds of anode current density-voltage curves under visible light of not sharing the same light;
Accompanying drawing 5 is TiO 2Nano-tube array and two kinds of anode electrochemical impedance spectroscopies under simulated solar irradiation of not sharing the same light.
Wherein: the TiO that T1 is to use ammonium fluoride to make 2Nano-tube array;
The TiO that T2 is to use hydrogen fluoride to make 2Nano-tube array;
P1 adopts electro-deposition at the TiO that uses ammonium fluoride to make 2Carry out the light anode that modified by silver obtains on the nanotube;
P2 adopts electro-deposition at the TiO that uses hydrogen fluoride to make 2Carry out the light anode that modified by silver obtains on the nanotube;
Embodiment
Embodiment 1
Present embodiment is a kind of TiO 2Nanotube array photo-anode is characterized in that, TiO 2The internal orifice dimension of nanotube is 70 ± 4nm, and tube wall is 20 ± 2nm, and pipe range is 1.946um.At described TiO 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
The preparation process of present embodiment is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut into little of 1cm * 5cm, and polishing is with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively; Ultrasonic power is 200 watts.
Step 2, preparation electrolyte: electrolyte is ammonium fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte.Wherein:
Ammonium fluoride electrolyte is made up of the ammonium fluoride of 0.25wt%, the deionized water of 2.5vol% and the ethylene glycol of 97.5vol%; Load weighted ammonium fluoride is placed beaker and adds deionized water, be stirred to ammonium fluoride and dissolve fully; Add ethylene glycol in being dissolved with the aqueous solution of ammonium fluoride, fully stirring mixes the aqueous solution of ammonium fluoride and ethylene glycol, obtains the mixed solution of ammonium fluoride and ethylene glycol; Use 2.0molL -1Sulfuric acid solution the mixed solution pH value of ammonium fluoride and ethylene glycol is transferred to 6, obtain ammonium fluoride electrolyte.
Silver nitrate electrolyte is by 0.05molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte.
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte.
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of HMP serial universal DC power supply is connected titanium foil, and negative pole connects platinum guaze; Ammonium fluoride electrolyte is imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under the ammonium fluoride liquid level of electrolyte, platinum guaze is immersed in the ammonium fluoride electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm; The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 17 ℃, and oxidation voltage is 30V, and oxidization time is 4h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array.
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed.
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize the CHI660C electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2Between nano-tube array and the platinum guaze at a distance of 2cm; Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 17 ℃, and sedimentation potential is-0.4V SCE, sedimentation time is 1min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
Embodiment 2
Present embodiment is a kind of TiO 2Nanotube array photo-anode is characterized in that, TiO 2The nanotube internal orifice dimension is 100 ± 10nm, and tube wall is 20 ± 4nm, and pipe range is 450 ± 30nm.At described TiO 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
The preparation process of present embodiment is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut into little of 1cm * 5cm, and polishing is with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively; Ultrasonic power is 200 watts.
Step 2, preparation electrolyte: electrolyte is hydrogen fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte.Wherein:
Hydrogen fluoride electrolyte is by 0.1molL -1Hydrogen fluoride and 2.0molL -1The mixed solution formed of sulfuric acid.Load weighted hydrogen fluoride is placed beaker and adds deionized water, be stirred well to hydrogen fluoride and deionized water mixes fully; Add sulfuric acid in being dissolved with the hydrofluoric aqueous solution, fully stirring mixes the hydrofluoric aqueous solution and sulfuric acid, obtains hydrogen fluoride electrolyte.
Silver nitrate electrolyte is by 0.1molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte.
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte.
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of HMP serial universal DC power supply is connected titanium foil, and negative pole connects platinum guaze; Hydrogen fluoride electrolyte is imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under the hydrogen fluoride liquid level of electrolyte, platinum guaze is immersed in the hydrogen fluoride electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm; The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 20 ℃, and oxidation voltage is 20V, and oxidization time is 1h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array.
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed.
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize the CHI660C electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2Between nano-tube array and the platinum guaze at a distance of 2cm; Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 20 ℃, and sedimentation potential is-0.6V SCE, sedimentation time is 2min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
Embodiment 3
Present embodiment is a kind of TiO 2Nanotube array photo-anode is characterized in that, TiO 2The internal orifice dimension of nanotube is 70 ± 4nm, and tube wall is 20 ± 2nm, and pipe range is 1.946um.At described TiO 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
The preparation process of present embodiment is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut into little of 1cm * 5cm, and polishing is with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively; Ultrasonic power is 200 watts.
Step 2, preparation electrolyte: electrolyte is ammonium fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte.Wherein:
Ammonium fluoride electrolyte is made up of the ammonium fluoride of 0.25wt%, the deionized water of 2.5vol% and the ethylene glycol of 97.5vol%; Load weighted ammonium fluoride is placed beaker and adds deionized water, be stirred to ammonium fluoride and dissolve fully; Add ethylene glycol in being dissolved with the aqueous solution of ammonium fluoride, fully stirring mixes the aqueous solution of ammonium fluoride and ethylene glycol, obtains the mixed solution of ammonium fluoride and ethylene glycol; Use 2.0molL -1Sulfuric acid solution the mixed solution pH value of ammonium fluoride and ethylene glycol is transferred to 6, obtain ammonium fluoride electrolyte.
Silver nitrate electrolyte is by 0.5molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte.
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte.
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of WYK D.C. regulated power supply is connected titanium foil, and negative pole connects platinum guaze; Ammonium fluoride electrolyte is imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under the ammonium fluoride liquid level of electrolyte, platinum guaze is immersed in the ammonium fluoride electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm; The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 25 ℃, and oxidation voltage is 30V, and oxidization time is 4h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array.
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed.
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize the CHI660C electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2At a distance of 2cm saturated calomel electrode is placed in the saturated potassium chloride electrolyte between nano-tube array and the platinum guaze, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 25 ℃, and sedimentation potential is-0.8V SCE, sedimentation time is 3min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
Embodiment 4
Present embodiment is a kind of TiO 2Nanotube array photo-anode is characterized in that, TiO 2The nanotube internal orifice dimension is 100 ± 10nm, and tube wall is 20 ± 4nm, and pipe range is 450 ± 30nm.At described TiO 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
The preparation process of present embodiment is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut into little of 1cm * 5cm, and polishing is with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively; Ultrasonic power is 200 watts.
Step 2, preparation electrolyte: electrolyte is hydrogen fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte.Wherein:
Hydrogen fluoride electrolyte is by 0.1molL -1Hydrogen fluoride and 2.0molL -1The mixed solution formed of sulfuric acid.Load weighted hydrogen fluoride is placed beaker and adds deionized water, be stirred well to hydrogen fluoride and deionized water mixes fully; Add sulfuric acid in being dissolved with the hydrofluoric aqueous solution, fully stirring mixes the hydrofluoric aqueous solution and sulfuric acid, obtains hydrogen fluoride electrolyte.
Silver nitrate electrolyte is by 1.0molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte.
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte.
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of WYK D.C. regulated power supply is connected titanium foil, and negative pole connects platinum guaze; Hydrogen fluoride electrolyte is imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under the hydrogen fluoride liquid level of electrolyte, platinum guaze is immersed in the hydrogen fluoride electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm; The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 30 ℃, and oxidation voltage is 20V, and oxidization time is 1h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array.
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed.
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize the CHI660C electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2Between nano-tube array and the platinum guaze at a distance of 2cm; Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 30 ℃, and sedimentation potential is-1.1V SCE, sedimentation time is 5min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
In order to characterize photovoltaic character, described modified by silver light anode has been carried out the photovoltaic property detection through modified by silver light anode.The photovoltaic property detection carries out at 17 ℃, uses CHI660C type electrochemical workstation to carry out data acquisition.Three-electrode system is adopted in test, promptly with modified by silver TiO 2Nanotube array photo-anode is a negative electrode, and platinum guaze is an anode, and saturated calomel is a reference electrode.Detailed process is that sodium sulphate electrolyte is imported in the quartz beaker; With platinum guaze with through modified by silver TiO 2Nanotube array photo-anode is vertically inserted in the beaker, and makes the titanium foil lower end immerse 1cm under the sodium sulphate liquid level of electrolyte, and platinum guaze is immersed in the sodium sulphate electrolyte fully; Through modified by silver TiO 2Between nanotube array photo-anode and the platinum guaze at a distance of 2cm.Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described sodium sulphate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in sodium sulphate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at process modified by silver TiO 2The short circuit current of nanotube array photo-anode-time graph testing apparatus.Use xenon lamp respectively simulated solar irradiation and visible light make radiation source, the light intensity of described analog light source is 100mWcm -2Adopt linear sweep voltammetry at short circuit current-time graph of measuring under two kinds of illumination, voltage range is-0.1～1.2Vsce; And simulated solar irradiation carries out the measurement of electrochemical impedance spectroscopy, and initial potential is elected 0.2Vsce as, and amplitude is 5mV, and frequency range is 100mHz～100kHz.

Claims (2)

1. TiO 2Nanotube array photo-anode is characterized in that, at described TiO 2There is silver-colored film on the nano-tube array surface; The microcosmic surface pattern of silver film is the dendrite of random distribution, and wherein a dendrite length is 6～15 μ m, and secondary dendrite length is 600nm～3 μ m, and the spacing between the secondary dendrite is 100～300nm.
2. one kind prepares TiO according to claim 1 2The method of nanotube array photo-anode is characterized in that, its concrete preparation process is as follows:
Step 1, handle the titanium foil matrix: titanium foil is cut slivering, polishing, with acetone, absolute ethyl alcohol and deionized water each ultrasonic waves for cleaning 5min successively, ultrasonic power is 200 watts;
Step 2, preparation electrolyte: electrolyte is ammonium fluoride electrolyte or hydrogen fluoride electrolyte, silver nitrate electrolyte, saturated potassium chloride electrolyte and sodium sulphate electrolyte; Wherein:
Ammonium fluoride electrolyte is made up of the ammonium fluoride of 0.25wt%, the deionized water of 2.5vol% and the ethylene glycol of 97.5vol%; Load weighted ammonium fluoride is placed beaker and adds deionized water, be stirred to ammonium fluoride and dissolve fully; Add ethylene glycol in being dissolved with the aqueous solution of ammonium fluoride, fully stirring mixes the aqueous solution of ammonium fluoride and ethylene glycol, obtains the mixed solution of ammonium fluoride and ethylene glycol; Use 2.0molL -1Sulfuric acid solution the mixed solution pH value of ammonium fluoride and ethylene glycol is transferred to 6, obtain ammonium fluoride electrolyte;
Hydrogen fluoride electrolyte is by 0.1molL -1Hydrogen fluoride and 2.0molL -1The mixed solution formed of sulfuric acid.Load weighted hydrogen fluoride is placed beaker and adds deionized water, be stirred well to hydrogen fluoride and deionized water mixes fully; Add sulfuric acid in being dissolved with the hydrofluoric aqueous solution, fully stirring mixes the hydrofluoric aqueous solution and sulfuric acid, obtains hydrogen fluoride electrolyte;
Silver nitrate electrolyte is by 0.05～1.0molL -1Silver nitrate, 0.1molL -1Potassium nitrate and 11.89gL -1The aqueous solution formed of polyethylene glycol; In beaker, add deionized water, load weighted polyethylene glycol, silver nitrate and potassium nitrate are added in the deionized water successively, be stirred to polyethylene glycol, silver nitrate and potassium nitrate and dissolve fully, obtain silver nitrate electrolyte; Saturated potassium chloride electrolyte is to add potassium chloride in deionized water, and constantly stirs, and no longer dissolves and has potassium chloride to separate out until potassium chloride, obtains saturated potassium chloride electrolyte;
Sodium sulphate electrolyte is 0.01molL -1Metabisulfite solution; In beaker, add deionized water, load weighted sodium sulphate is added in the deionized water, be stirred well to sodium sulphate and dissolve fully, obtain sodium sulphate electrolyte;
Step 3, preparation TiO 2Nano-tube array: adopt anode oxidation method at titanium foil surface preparation TiO 2Nano-tube array; The positive pole of DC power supply is connected titanium foil, and negative pole connects platinum guaze; Ammonium fluoride electrolyte or hydrogen fluoride electrolyte are imported in the beaker; Titanium foil and platinum guaze are vertically placed in the beaker, and make the titanium foil lower end immerse 1cm under ammonium fluoride electrolyte or the hydrogen fluoride liquid level of electrolyte, platinum guaze is immersed in the described electrolyte fully; Between titanium foil and the platinum guaze at a distance of 2cm;
The beaker that titanium foil and platinum guaze are housed is placed on the constant temperature blender with magnetic force, obtains preparing TiO 2The anodic oxidation device of nano-tube array utilizes this device that titanium foil is carried out anodic oxidation; Oxidizing temperature is 17～30 ℃; Use ammonium fluoride electrolyte at titanium foil surface preparation TiO 2During nano-tube array, oxidation voltage is 30V, and oxidization time is 4h; Use hydrogen fluoride electrolyte at titanium foil surface preparation TiO 2During nano-tube array, oxidation voltage is 20V, and oxidization time is 1h; After oxidation finishes, with the titanium foil of washed with de-ionized water through peroxidating; To put into resistance furnace behind the titanium foil natural air drying of peroxidating calcines; Calcining heat is 500 ℃, and calcining 1h with the stove cooling, obtains TiO 2Nano-tube array;
Step 4, preparation salt bridge: the potassium nitrate of 90g is dissolved in the 100g deionized water, solution is heated to 60 ℃ and insulation, obtain potassium nitrate solution by water-bath; Adding quality in potassium nitrate solution is the agar of 9.5g, is warming up to the agar that 90 ℃ of dissolvings are added; Solution is poured in the U-shaped glass tube, naturally cool to 20 ℃, promptly form the salt bridge that potassium nitrate and agar solid mixture are housed;
Step 5 is at TiO 2Nano-tube array surface electrical depositing silver: utilize electrochemical workstation, with TiO 2Nano-tube array is a work electrode, and platinum guaze is an auxiliary electrode, and saturated calomel is a reference electrode, at TiO 2Nano-tube array surface electrical depositing silver; Detailed process is that silver nitrate electrolyte is imported in the beaker; With platinum guaze with through TiO 2Nano-tube array is vertically inserted in the beaker, and makes TiO 21cm under the silver nitrate liquid level of electrolyte is immersed in the nano-tube array lower end, and platinum guaze is immersed in the silver nitrate electrolyte fully; TiO 2Between nano-tube array and the platinum guaze at a distance of 2cm; Saturated calomel electrode is placed in the saturated potassium chloride electrolyte, described silver nitrate electrolyte is connected with saturated potassium chloride electrolyte by salt bridge; During connection, the two ends of salt bridge are immersed in silver nitrate electrolyte and the saturated potassium chloride electrolyte respectively, obtain at TiO 2The device of nano-tube array surface electrical depositing silver; At TiO 2During nano-tube array surface electrical depositing silver, depositing temperature is 17 ℃～30 ℃, sedimentation potential is-0.4～-1.1V SCE, sedimentation time is 1～5min, obtains the TiO through modified by silver 2Nanotube array photo-anode.
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