CN105374566A - Preparation method of titanium dioxide photo-anode - Google Patents
Preparation method of titanium dioxide photo-anode Download PDFInfo
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- CN105374566A CN105374566A CN201510651925.7A CN201510651925A CN105374566A CN 105374566 A CN105374566 A CN 105374566A CN 201510651925 A CN201510651925 A CN 201510651925A CN 105374566 A CN105374566 A CN 105374566A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 81
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 79
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 59
- 230000003647 oxidation Effects 0.000 claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005282 brightening Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 abstract description 46
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000007781 pre-processing Methods 0.000 abstract 4
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 abstract 1
- 238000003466 welding Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000007743 anodising Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000319 cold-field-emission scanning electron microscopy Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Hybrid Cells (AREA)
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Abstract
The invention provides a preparation method of a titanium dioxide photo-anode. The preparation method comprises the steps of: firstly carrying out pre-processing on titanium sheets, obtaining the titanium sheets after the preprocessing, and then welding the titanium sheets after the preprocessing with a conductive wire; using the titanium sheets after the preprocessing as a cathode and an anode, placing the cathode and the anode in an electrolyte, and then applying a direct-current voltage between the cathode and the anode for oxidation, wherein the oxidized anode titanium sheet is a metal titanium-titanium dioxide nano-tube array composite material; and carrying out heat treatment on the oxidized composite material, and obtaining the titanium dioxide photo-anode. According to the method, the anode and the cathode in the preparation process are respectively a titanium sheet, a 20-60 V direct-current voltage is applied between the anode and the cathode for oxidation, and the oxidation time is 20-60 min, so that the oxidation time is shortened, the oxidation voltage is lowered, the prepared titanium dioxide photo-anode has a uniform and orderly nano-tube array structure, the photoelectric property is high and uniform, and the photocurrent density is high and is strong in repeatability.
Description
Technical field
The invention belongs to technical field of solar batteries, relate to a kind of preparation method of smooth anode, be specifically related to a kind of preparation method of titanium dioxide photo anode.
Background technology
The light anode of current DSSC (DSCs) mainly adopts nano titanium oxide (TiO
2) be base material, comprise nano-TiO
2film and TiO
2nano-tube array two type.Wherein, the TiO utilizing anode oxidation method to prepare
2nanotube is perpendicular to substrate and have larger specific area, its nano-tube array structure is conducive to the diffusion at semiconductive thin film and electrolyte interface of the transmission of light induced electron and ion, therefore plays more and more important effect in fields such as DSSC (DSCs).
Anode oxidation method is generally that negative electrode commonly uses platinum electrode using metal titanium sheet as anode, and the inert materials such as lead, copper and graphite also once had to use to be reported; Obtained TiO is carried out by applying voltage between the cathode and anode being placed in specific electrolyte
2nano-tube array.Other nano-TiOs relatively
2preparation method, anode oxidation method material therefor is more, technique relative complex and consuming time.In addition, TiO is prepared about anodic oxidation at present
2research and experiment be all difficult to realize TiO
2the consistency that photoelectric properties are higher in good uniformity and different sample in same sample, this affects the use of the method in DSCs to a great extent.
Therefore, need conventional anodes oxidizing process Simplified flowsheet, simultaneously to improve TiO
2optic-electronic Stabilization is qualitative is target improving technique parameter.
Summary of the invention
Therefore, the object of the invention is a kind of preparation method of titanium dioxide photo anode, thus the preparation process of titanium dioxide anode can be simplified, oxidization time is short, and cost-saving, and titanium dioxide photo anode prepared by the method has higher and uniform photoelectric properties, and density of photocurrent is high.
On the one hand, the invention provides a kind of preparation method of titanium dioxide photo anode, comprise the following steps:
1) first titanium sheet is carried out preliminary treatment, obtain pretreated titanium sheet, then by pretreated titanium sheet and wire bonds;
2) described pretreated titanium sheet is got as negative electrode and anode, again described negative electrode and anode are placed in electrolyte, then between described negative electrode and anode, apply direct voltage oxidation 20 ~ 60min, anode titanium sheet (being the composite material existed with Titanium-Nano tube array of titanium dioxide form) after oxidation, described direct voltage is 20 ~ 60V, described electrolyte is without water glycol electrolyte, described without the NH containing 0.125 ~ 0.50Wt% in water glycol electrolyte
4f;
3) then by the anode titanium sheet heat treatment after described oxidation, obtain titanium dioxide photo anode, to obtain final product.
Preferably, in step 2) in, described direct voltage is 20 ~ 40V, and the nanotube being oxidized the light anode material obtained under the direct voltage within the scope of this is fairly perfect, and aligns mutually, and photoelectric conversion Performance comparision is high, and density of photocurrent is higher.
More preferably, described direct voltage is 20V, is oxidized the light anode material density of photocurrent obtained the highest under this direct voltage.
Preferably, in step 2) in, direct voltage oxidation 30 ~ 60min is applied between described negative electrode and anode, the titanium dioxide photo anode of difference on preparation of anodizing time has impact, the time too short or long photoelectric conversion performance that all can reduce titanium dioxide photo anode, the photoelectric conversion performance of titanium dioxide photo anode obtained within the scope of this oxidization time improves gradually, but oxidization time is higher than after 60min, can cause that nanotube growth is long and avalanche comes off and extent of corrosion strengthens, the randomness of nano-tube array increases, thus make its photoelectric conversion hydraulic performance decline, but the nanotube formed within the scope of 30 ~ 60min is fairly perfect, and align mutually, photoelectric conversion Performance comparision is high.
More preferably, direct voltage oxidation oxidation 40min is applied between described negative electrode and anode, the photoelectric properties of the titanium dioxide photo anode that this oxidization time obtains are the highest, and preparation titanium dioxide photo anode nanotube also non-avalanche come off, Nanotube alignment straight uniform.
Preferably, in step 2) in, described without the NH containing 0.125 ~ 0.375Wt% in water glycol electrolyte
4f, anodised electrolyte concentration difference also has impact to preparing titanium dioxide photo anode, too low or the too high photoelectric conversion performance that all can reduce titanium dioxide photo anode of electrolyte concentration, electrolytical concentration is higher than after 0.25Wt%, nanotube extent of corrosion can be caused to strengthen, also its randomness is made to increase, thus its photoelectric conversion performance is declined gradually, but the nanotube formed within the scope of 0.125 ~ 0.375Wt% is fairly perfect, and align mutually, photoelectric conversion Performance comparision is high, therefore the photoelectric conversion performance of titanium dioxide photo anode that obtains at this concentration range internal oxidition of electrolyte is higher.
More preferably, described without the NH containing 0.25Wt% in water glycol electrolyte
4f, containing this concentration electrolyte solution, obtained titanium dioxide photo anode has the highest photoelectric conversion performance, and the Nanotube alignment straight uniform of the titanium dioxide photo anode of preparation.
Further preferably, described without the H of volume % also containing 0.02 in water glycol electrolyte
2o.
Preferably, in step 2) in, after obtaining the anode titanium sheet after being oxidized, also comprise the anode titanium sheet after by described oxidation and first rinse with water, then carry out dry step.
Preferably, in step 3) in, the heat treatment 90min at 450 DEG C of the anode titanium sheet after described oxidation.
Preferably, in step 1) in, described titanium sheet carries out preliminary treatment by the method comprised the steps: first by the ultrasonic cleaning of titanium sheet absolute ethyl alcohol, then use deionized water ultrasonic cleaning, obtain the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, then use chemical brightening solution polishing 5 ~ 10S, finally use deionized water rinsing dry, obtain pretreated titanium sheet.
The preparation method of titanium dioxide photo anode of the present invention, preparing Anodic and negative electrode all adopts titanium sheet, and the direct voltage applying 20 ~ 60V in this preparation method is between the anode and cathode oxidized, oxidization time only has 20 ~ 60min, and in prior art general oxidization time be 2 ~ 48h not etc., what have even will be oxidized several days, therefore achieve at shorter oxidization time with comparatively under suboxides voltage conditions, the titanium dioxide photo anode of preparation has evenly neat nano-tube array structure, photoelectric properties are high and even, density of photocurrent is high and by force repeated, and shown by test, by the preparation method of the application, just the titanium sheet as negative electrode is replaced by Pt, the nanotube surface of its titanium dioxide photo anode prepared is attached with the particulate material of larger area, cause nano-tube array not evenly complete, and the combination of particulate matter and nanotube is very loose, the conduction efficiency of light induced electron is reduced greatly, thus its titanium dioxide photo anode has lower density of photocurrent, illustrate that the application is by preparing titanium dioxide photo anode by titanium sheet as negative electrode and anode simultaneously, unexpectedly obtain optical density high, the titanium dioxide photo anode that photoelectric properties are high, and the metal using other instead can not obtain the titanium dioxide photo anode of same optical density and photoelectric properties by this method as negative electrode, simultaneously method of the present invention avoids introducing and the interference of other materials in oxidation system to a certain extent, and relative to the Pt electrode that conventional anodes oxidizing process is conventional, Ti raw material relative moderate is easy to get, and convenient operation and adjustment.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 a is the scanning electron microscope (SEM) photograph of titanium dioxide photo anode of the present invention under 3 μm of scale range;
Fig. 1 b is the electron-microscope scanning figure of titanium dioxide photo anode of the present invention under 15 μm of scale range;
Fig. 1 c is the electron-microscope scanning figure of titanium dioxide photo anode of the present invention under 0.26mm scale range;
Fig. 2 is the density of photocurrent collection of illustrative plates of titanium dioxide photo anode prepared by three groups of anodic oxidation parallel tests of the present invention;
Fig. 3 is the density of photocurrent figure of titanium dioxide photo anode prepared by different anodizing time of the present invention;
When Fig. 4 is anodic oxidation of the present invention, the oxidation electrolyte of variable concentrations prepares the density of photocurrent figure of titanium dioxide photo anode;
The density of photocurrent figure of titanium dioxide photo anode is prepared under different oxidation voltage when Fig. 5 is anodic oxidation of the present invention;
When Fig. 6 is anodic oxidation of the present invention, the density of photocurrent collection of illustrative plates of titanium dioxide photo anode prepared by different cathode material;
When Fig. 7 is anodic oxidation of the present invention, Pt metal does the scanning electron microscope (SEM) photograph of titanium dioxide photo anode prepared by negative electrode.
Embodiment
Unless specifically stated otherwise, reagent used in following examples all can be commercially available from regular channel.
Unless specifically stated otherwise, metal titanium sheet used in following examples is the titanium sheet of purity >99.5%.
embodiment 1
First metal titanium sheet is cut into 20mm × 40mm × 0.1mm size, then metal titanium sheet is first used absolute ethyl alcohol ultrasonic cleaning, then use deionized water ultrasonic cleaning, obtain the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, (polishing fluid is V (HF): the V (HNO of 1:4:5 by volume ratio to use chemical brightening solution afterwards
3): V (H
2o) form) polishing 5S, obtain pretreated titanium sheet after drying; Get the pretreated titanium sheet of two panels again respectively as negative electrode and anode, and connect with stainless steel traverse point is soldered, and then be placed in containing 0.25Wt%NH
4f, 0.02 volume %H
2o without in water glycol electrolyte (and make stainless steel wire not with electrolyte contacts), 60V direct voltage is applied between anode and cathode, oxidization time 40min, put into rotor when anodic oxidation is carried out in the electrolytic solution and stir, rotating speed remains on below 60rad/min; Get anode titanium sheet pure water rinsing and air drying, obtain the anode titanium sheet after being oxidized (being the composite material existed with Titanium-Nano tube array of titanium dioxide form), then be put in Muffle furnace, in 450 DEG C of heating 90min, titanium dioxide photo anode.
By the titanium dioxide photo anode obtained, under ESEM (Hitachi cold field emission scanning electron microscopy JSM-7500F), observe, result as illustrated in figures la-c, visible by Fig. 1 a (× 50,000), TiO prepared under the method according to the invention
2tube diameters is about 50nm, and array arranges evenly in 3 μm of scale range, and material surface area significantly increases; All visible by Fig. 1 b (× 10,000) and Fig. 1 c (× 500), sample 15 μm, still there is evenly neat nano-tube array structure in 0.26mm scale range.
Be to electrode with simple metal Pt sheet, Na
2sO
4solution is electrolyte, solar cell is assembled into titanium dioxide photo anode, 450WXe lamp, the U.S.'s wide scientific and technological CT110 monochromator of chin or cheek and U.S. A Meiteke PARSTAT2273 potentiostat photoelectricity is adopted to be used in conjunction test macro, the monochromatic light ray current density collection of illustrative plates of METHOD FOR CONTINUOUS DETERMINATION three groups of samples, result as shown in Figure 2.
As seen from Figure 2, when without dye sensitization, the density of photocurrent of sample reaches as high as 114.55 μm/cm
-2, and between many group samples, there is very high consistency.
the different oxidization time of embodiment 2 prepares titanium dioxide photo anode
First metal titanium sheet is cut into 20mm × 40mm × 0.1mm size, then metal titanium sheet is first used absolute ethyl alcohol ultrasonic cleaning, then use deionized water ultrasonic cleaning, obtain the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, (polishing fluid is V (HF): the V (HNO of 1:4:5 by volume ratio to use chemical brightening solution afterwards
3): V (H
2o) form) polishing 10S, obtain pretreated titanium sheet after drying; Get the pretreated titanium sheet of two panels again respectively as negative electrode and anode, and connect with stainless steel traverse point is soldered, and then be placed in containing 0.25Wt%NH
4f, 0.02 volume %H
2o without water glycol electrolyte (and make stainless steel wire not with electrolyte contacts) in, between cathode and anode, apply 20V direct voltage, oxidization time 40min; Get anode titanium sheet pure water rinsing and air drying, obtain the anode titanium sheet after being oxidized and (be the composite material existed with Titanium-Nano tube array of titanium dioxide form, then be put in Muffle furnace, in 450 DEG C of heating 90min, obtained titanium dioxide photo anode.
In addition, in said process, other conditions remain unchanged, and only anodizing time are changed to 10min, 20min, 30min, 60min and 90min by 40min, obtained other five kinds of titanium dioxide photo anodes.
Six kinds of different titanium dioxide photo anodes of preparation are assembled into solar cell with other materials respectively, pass through 8.4mW/cm
2tungsten lamp illumination condition and U.S.'s A Meiteke PARSTAT2273 potentiostat measure the density of photocurrent under its open circuit voltage, and result as shown in Figure 3.
As seen from Figure 3, the difference of anodizing time has considerable influence to preparing titanium dioxide photo anode, oxidization time is too short, and Nano tube array of titanium dioxide structure does not also generate completely or generates imperfection, as in experiment, the oxidization time of 10min does not form nano-tube array; The nanotube formed in 30-60min is fairly perfect, and align mutually, photoelectric conversion Performance comparision is high, oxidization time then can cause that nanotube growth is long more than 60min and avalanche comes off, surface corrosion obviously, randomness increases, time, longer meeting cannot use because avalanche is more serious, and both all can reduce the photoelectric conversion performance of titanium dioxide photo anode.When being oxidized 40min, TiO
2nano-tube array growth is complete, is combined closely with metal Ti, and nano-tube array order is strong, therefore has the highest density of photocurrent value.
embodiment 3 variable concentrations electrolyte solution prepares titanium dioxide photo anode
By metal titanium sheet with first using absolute ethyl alcohol ultrasonic cleaning, then using deionized water ultrasonic cleaning, obtaining the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, (polishing fluid is V (HF): the V (HNO of 1:4:5 by volume ratio to use chemical brightening solution afterwards
3): V (H
2o) form) polishing 8S, obtain pretreated titanium sheet after drying; Get the pretreated titanium sheet of two panels again respectively as negative electrode and anode, and connect with stainless steel traverse point is soldered, and then be placed in containing 0.25Wt%NH
4f, 0.02 volume %H
2o without water glycol electrolyte (and make stainless steel wire not with electrolyte contacts) in, between anode and cathode, apply 20V direct voltage, oxidization time 40min; Get anode titanium sheet pure water rinsing and air drying, obtain the anode titanium sheet after being oxidized and (be the composite material existed with Titanium-Nano tube array of titanium dioxide form, then be put in Muffle furnace, in 450 DEG C of heating 90min, obtained titanium dioxide photo anode.
In said process, other conditions remain unchanged, and only NH4F concentration in anode oxidation process electrolyte are changed to 0.08Wt%, 0.125Wt%, 0.375Wt%, 0.50Wt% and 0.625Wt% by 0.25Wt%, obtained other five kinds of titanium dioxide photo anodes.
Six kinds of different titanium dioxide photo anodes of preparation are assembled into solar cell with other materials respectively, pass through 8.4mW/cm
2tungsten lamp illumination condition and U.S.'s A Meiteke PARSTAT2273 potentiostat measure the density of photocurrent under its open circuit voltage), result is as shown in Figure 4.
As seen from Figure 4, anodised electrolyte concentration is different consistent with oxidization time on the impact preparing titanium dioxide photo anode, and electrolyte concentration is too low (lower than 0.1Wt%, as the NH of 0.08Wt% in experiment
4f does not form nano-tube array) nano-tube array structure imperfection can be caused maybe cannot to be formed, too high (higher than 0.50Wt%) all can cause that nano-tube array structure avalanche comes off, surface corrosion obviously, randomness increases gradually, thus reduce the photoelectric conversion performance of titanium dioxide photo anode, the nanotube that electrolyte concentration is formed within the scope of 0.125 ~ 0.375Wt% is fairly perfect, and align mutually, photoelectric conversion Performance comparision is high.When electrolyte concentration is 0.25Wt%, TiO
2nano-tube array growth is neatly complete, is combined closely with metal Ti, and order is strong, and obtained titanium dioxide photo anode has the highest photoelectric conversion value.
under the different direct voltage of embodiment 4, titanium dioxide photo anode is prepared in oxidation
By metal titanium sheet with first using absolute ethyl alcohol ultrasonic cleaning, then using deionized water ultrasonic cleaning, obtaining the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, (polishing fluid is V (HF): the V (HNO of 1:4:5 by volume ratio to use chemical brightening solution afterwards
3): V (H
2o) form) polishing 10S, obtain pretreated titanium sheet after drying; Get the pretreated titanium sheet of two panels again respectively as negative electrode and anode, and connect with stainless steel traverse point is soldered, and then be placed in containing 0.25Wt%NH
4f, 0.02 volume %H
2o without water glycol electrolyte (and make stainless steel wire not with electrolyte contacts) in, between anode and cathode, apply 20V direct voltage, oxidization time 40min; Get anode titanium sheet pure water rinsing and air drying, obtain the anode titanium sheet after being oxidized and (be the composite material existed with Titanium-Nano tube array of titanium dioxide form, then by it in 450 DEG C of heating 90min, obtain titanium dioxide photo anode.
In said process, other conditions remain unchanged, and only anodic oxidation oxidation voltage are changed to 10V, 40V, 60V and 80V by 20V, obtained other four kinds of titanium dioxide photo anodes.Five kinds of different titanium dioxide photo anodes of preparation are assembled into solar cell with other materials respectively, pass through 8.4mW/cm
2tungsten lamp illumination condition and U.S.'s A Meiteke PARSTAT2273 potentiostat measure the density of photocurrent under its open circuit voltage, and result as shown in Figure 5.
As seen from Figure 5, oxidation voltage has a certain impact to preparing the same tool of titanium dioxide photo anode.Under other process conditions uniform conditions of maintenance the present invention, the TiO2 light anode obtained during oxidation voltage 20V has the highest density of photocurrent value, can cause the TiO generated lower than 20V
2nano-tube array imperfection maybe cannot be formed, nano-tube array is not formed under oxidization time as 10V in experiment, and when oxidation voltage is higher than after during 20V, titania nanotube diameter then can be made excessive and damaged or cave in gradually, randomness increases gradually, higher than more than 60V, the randomness of titania nanotube is more and more stronger, order worse and worse, its light anode density of photocurrent is declined thereupon, direct voltage is 20 ~ 40V, the nanotube being oxidized the light anode material obtained under direct voltage within the scope of this is fairly perfect, and align mutually, photoelectric conversion Performance comparision is high, density of photocurrent is higher.
comparative example 1
By metal titanium sheet with first using absolute ethyl alcohol ultrasonic cleaning, then using deionized water ultrasonic cleaning, obtaining the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, (polishing fluid is V (HF): the V (HNO of 1:4:5 by volume ratio to use chemical brightening solution afterwards
3): V (H
2o) form) polishing 10S, obtain pretreated titanium sheet after drying; Again by pretreated titanium sheet and stainless steel traverse point is soldered connects.Using above-mentioned titanium sheet as anode and negative electrode, be placed in containing 0.25Wt%NH
4f, 0.02 volume %H
2o without water glycol electrolyte (and make stainless steel wire not with electrolyte contacts) in, between anode and cathode, apply 20V direct voltage, oxidization time 40min; Pure water rinsing air drying, obtain the anode titanium sheet after being oxidized and (be the composite material existed with Titanium-Nano tube array of titanium dioxide form, then by it in 450 DEG C of heating 90min, obtain titanium dioxide photo anode.
In said process, other conditions remain unchanged, and only negative electrode during anodic oxidation are changed to platinum electrode by metal titanium sheet, and another titanium dioxide photo anode obtained, under Electronic Speculum, scan this obtained titanium dioxide photo anode, result as shown in Figure 7.Three kinds of different titanium dioxide photo anodes of preparation are assembled into solar cell with other materials respectively, and measure its density of photocurrent collection of illustrative plates, result as shown in Figure 6.
By Fig. 7 finding, the TiO that Pt metal is prepared as negative electrode
2nanotube surface is attached with the particulate material of larger area, cause nano-tube array not evenly complete, and the combination of particulate matter and nanotube is very loose, the conduction efficiency of light induced electron is reduced greatly, thus the light anode that the titanium dioxide photo anode causing this method to be prepared is prepared relative to the present invention has lower density of photocurrent, as shown in Figure 6.Thus illustrate, under the method according to the invention, anode and negative electrode all adopt titanium sheet, shorten oxidization time, reduce oxidation voltage, and the titanium dioxide anode of preparation has evenly neat nano-tube array structure, and photoelectric properties are high and even.
Claims (10)
1. a preparation method for titanium dioxide photo anode, comprises the following steps:
1) first titanium sheet is carried out preliminary treatment, obtain pretreated titanium sheet, then by pretreated titanium sheet and wire bonds;
2) described pretreated titanium sheet is got as negative electrode and anode, again described negative electrode and anode are placed in electrolyte, then between described negative electrode and anode, apply direct voltage oxidation 20 ~ 60min, obtain the anode titanium sheet after being oxidized, described direct voltage is 20 ~ 60V, described electrolyte is without water glycol electrolyte, described without the NH containing 0.125 ~ 0.50Wt% in water glycol electrolyte
4f;
3) then by the anode titanium sheet heat treatment after described oxidation, obtain titanium dioxide photo anode, to obtain final product.
2. the preparation method of titanium dioxide photo anode according to claim 1, is characterized in that, in step 2) in, described direct voltage is 20 ~ 40V.
3. the preparation method of titanium dioxide photo anode according to claim 2, is characterized in that, described direct voltage is 20V.
4. the preparation method of titanium dioxide photo anode according to claim 1, is characterized in that, in step 2) in, between described negative electrode and anode, apply direct voltage oxidation 30 ~ 60min.
5. the preparation method of titanium dioxide photo anode according to claim 4, is characterized in that, applies direct voltage oxidation 40min between described negative electrode and anode.
6. the preparation method of titanium dioxide photo anode according to claim 1, is characterized in that, in step 2) in, described without the NH containing 0.125 ~ 0.375Wt% in water glycol electrolyte
4f.
7. the preparation method of titanium dioxide photo anode according to claim 6, is characterized in that, described without the NH containing 0.25Wt% in water glycol electrolyte
4f; Preferably, described without the H of volume % also containing 0.02 in water glycol electrolyte
2o.
8. the preparation method of titanium dioxide photo anode according to any one of claim 1 to 7, is characterized in that, in step 2) in, after obtaining the anode titanium sheet after being oxidized, also comprise and described anode titanium sheet is first rinsed with water, then carry out dry step.
9. the preparation method of titanium dioxide photo anode according to any one of claim 1 to 7, is characterized in that, in step 3) in, the heat treatment 90min at 450 DEG C of the anode titanium sheet after described oxidation.
10. the preparation method of titanium dioxide photo anode according to any one of claim 1 to 7, it is characterized in that, in step 1) in, described titanium sheet carries out preliminary treatment by the method comprised the steps: first by the ultrasonic cleaning of titanium sheet absolute ethyl alcohol, use deionized water ultrasonic cleaning again, obtain the titanium sheet of ultrasonic cleaning; Again that the titanium sheet after ultrasonic cleaning is dry, then use chemical brightening solution polishing 5 ~ 10S, finally use deionized water rinsing dry, obtain pretreated titanium sheet.
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