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CN1763261A - A kind of titanium oxide nanomaterial thin film and preparation method thereof - Google Patents

A kind of titanium oxide nanomaterial thin film and preparation method thereof Download PDF

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CN1763261A
CN1763261A CN 200510086520 CN200510086520A CN1763261A CN 1763261 A CN1763261 A CN 1763261A CN 200510086520 CN200510086520 CN 200510086520 CN 200510086520 A CN200510086520 A CN 200510086520A CN 1763261 A CN1763261 A CN 1763261A
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film
titanium oxide
deposition
preparation
cathode
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CN100417749C (en
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林红
王宁
林春富
李建保
杨晓战
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QINGDAO BLACK GOLD THERMAL ENERGY Co Ltd
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Tsinghua University
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Abstract

The present invention is nanometer titania film and its preparation process, and belongs to low-dimensional nanometer material technology. In the electrochemical deposition process, nanometer titania powder, surfactant, anhydrous ethanol and metal salt as electrolyte are mixed and ultrasonic dispersed to obtain homogeneously dispersed stable suspension. By means of stainless steel or nickel sheet as anode, transparent conducting ITO glass or transparent conducting FTO polymer as depositing cathode, and constant voltage power source, nanometer titania film is deposited on the cathode substrate at room temperature. The deposited film is then heat treated at 400-550 deg.c or microwave treated for 1-3 hr. The process has easy control and low temperature, and the deposited nanometer titania film has flat surface, high porosity, great specific area and low cost. The present invention is suitable for industry production of dye sensitized solar cell film material.

Description

A kind of titanium dioxide nano material film and preparation method thereof
Technical field
The invention belongs to the low-dimension nano material film preparation, particularly a kind of electrophoretic deposition prepares the preparation method of all controlled titanium dioxide nano material film of thickness, aperture, porosity.
Background technology
The TiOx nano crystallized semiconductor thin film of broad-band gap is a kind of marvellous material, and they show special optics and electric property, are widely used in photochemical catalysis, electroluminescent and photoelectric device.1991, Switzerland scientist Gratzel invented a kind of solar cell-dye sensitization solar battery (DSSC) of new ideas, causes various countries scientist's extensive concern and attention immediately.It mainly contains 5 parts and forms: transparency conductive electrode, titanium oxide porous membrane, the dye molecule that is adsorbed, ionogen, platinum plating counter electrode.Its working mechanism is: dye molecule absorbs photon and produces electron-hole pair, the electronics of excited state spreads in the titanium oxide porous membrane through the titanium oxide conduction band, enters external circuit, and the hole then enters electrolytical lumo energy, in ionogen, transmit, and then enter external circuit.Compare with traditional Si solar cell, the generation in electronics-hole of DSSC is to carry out in different materials with transmission, thereby recombination probability is little, purity requirement to material is not high, thereby cost only is 1/5～1/10 of Si battery, and this is expected to promote greatly the extensive civil nature process of photovoltaic product.Traditionally, the photo-anode film of preparation dye sensitization solar battery mainly adopts hand to be coated with method and silk screen print method, it is very poor that hand is coated with the thin film stability of method preparation, obviously is not suitable for scale operation, and silk screen print method is had relatively high expectations to experimental installation and also is unfavorable for scale production.
Electrophoretic deposition can be effectively at conductive substrates surface deposition porous membrane, thickness, uniformity coefficient and the sedimentation rate of its energy better controlled film.Electrophoretic deposition is the most attracting to be owing to it is very low to raw material and not high its preparation cost that makes of equipment requirements, is very suitable for scale operation.In addition, electrophoretic deposition can be realized film formation at low temp easily, thereby it is preparation flexible solar battery anodic good method, and this can expand the Application Areas of dye sensitization solar battery greatly.
Characteristics according to dye sensitization solar battery technology of preparing and electrophoretic deposition, this paper has invented and has a kind ofly prepared the technology of preparing of various titanium dioxide nano material films with electrophoretic deposition, and it is simple that this technology has synthetic method, and cost is low, but film formation at low temp is fit to many advantages such as scale operation.
Summary of the invention
The object of the present invention is to provide all controlled titanium dioxide nano material film of a kind of thickness, aperture, porosity and preparation method thereof.
A kind of titanium dioxide nano material film of the present invention and preparation method thereof, adopt electrophoretic deposition, it is characterized in that: described method is with behind titanium dioxide nano material powder, tensio-active agent, the dehydrated alcohol uniform mixing, do ionogen with metallic salt, through ultra-sonic dispersion, fully stir that the back obtains to disperse, even, stable titanium dioxide nano material suspension; Do anode with deposition substrate anode stainless steel, nickel sheet, aluminium flake, platinized platinum, conductive glass, conducting high polymers thing, transparent ITO conductive glass, transparent FTO conductive glass, transparent flexible ITO polymkeric substance, transparent FTO conductive polymers is as deposition cathode, and constant voltage power supply is as electric supply installation.The chamber at room temperature, deposition voltage is 2～100V/cm, depositing time is 0.2～60 minute, deposits surfacing at last on cathode substrate, is uniformly dispersed the titanium dioxide nano material film that aperture, porosity, thickness are all controlled.This film is handled 1～3h through 400 ℃～550 ℃ thermal treatments or low-temperature microwave again, obtains final titanium dioxide nano material film; Its technological process is:
(1) tensio-active agent is put into dehydrated alcohol, ultrasonic, tensio-active agent is fully dissolved, the add-on of described tensio-active agent is 0.1～6wt%;
(2) be that 5～40% titanium dioxide nano material and 0.1～8wt% metallic salt ionogen are put into solution respectively with volume fraction, ultrasonic agitation is even;
(3) do anode with stainless steel, nickel sheet, aluminium flake, platinized platinum, conductive glass, conducting high polymers thing, with cleaned electrically conducting transparent substrate is negative electrode, negative electrode and anode spacing are from being 0.3～3 centimetre, constant voltage power supply is as electric supply installation, deposition voltage is 2～100V/cm, and depositing time is 0.2～60 minute, obtains surfacing on cathode substrate, be uniformly dispersed, thickness is the thin film of titanium oxide of 1～20 μ m.
(4) film of step 3 is handled 1～3h through 400 ℃～550 ℃ thermal treatments or low-temperature microwave again, obtain final titanium dioxide nano material film.
In above-mentioned preparation method, titanium dioxide nano material is the TiOx nano crystalline substance in the described reaction raw materials, titanium oxide nanotubes, TiOx nano line.
In above-mentioned preparation method, described tensio-active agent is a polyvinyl butyral acetal, polyvinyl alcohol, sodium lauryl sulphate, hexadecyl trimethyl ammonium bromide, the various negatively charged ion of polyethenoxy ether class, positively charged ion, non-polar surfactant.
In above-mentioned preparation method, described metallic salt ionogen is Ti (SO 4) 2, Zn (NO 3) 2, Ni (NO 3) 2, Al (NO 3) 3, ZnCl 2Various metallic salts.
The present invention has the following advantages:
1, adopt electrophoretic deposition method, can be extensive, low-cost preparation dye-sensitized solar cell anode film.
2, adopt various tensio-active agents to make the vesicular structure that dispersion agent and pore-forming material can effectively be controlled film.
3, adopt transparent ITO conductive glass, transparent FTO conductive glass, transparent flexible ITO polymkeric substance, transparent FTO conductive polymers can obtain all titanium dioxide nano material films of even controllable thickness of surface as deposition cathode.
4, adopt metallic salt to do the electrophoretic deposition ionogen and can effectively improve sedimentation velocity, and the neck of strengthening between the nanoparticle connects.
5, adopt the microwave treatment titanium dioxide nano material film, but low temperature is removed organic impurity, effectively promotes the industrialization of flexible dye-sensitized solar battery, and then expands its use range.
Description of drawings
Fig. 1 is the SEM figure (cross section) of the brilliant film of resultant electrophoretic deposition TiOx nano.
Fig. 2 is the SEM figure of resultant electrophoretic deposition titanium oxide nanotubes film.
Fig. 3 does the structural representation of light anode dye sensitization solar battery for the electrophoretic deposition titanium dioxide nano material film
Fig. 4 does the IV curve of light anode dye sensitization solar battery for the brilliant film of resultant electrophoretic deposition TiOx nano.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
Titanium dioxide nano material (titanium oxide nanotubes in volume fraction 5～40%, the TiOx nano crystalline substance, the TiOx nano rod) in the suspension, add 0.1～6wt% tensio-active agent and do dispersion agent, after powerful stirring, excusing from death disperse, (0.1～8wt%) does ionogen with metallic salt, do anode with stainless steel, nickel sheet, aluminium flake, platinized platinum, conductive glass, conducting high polymers thing, transparent ITO conductive glass, transparent FTO conductive glass, transparent flexible ITO polymkeric substance, transparent FTO conductive polymers is as deposition cathode.The aperture of film and porosity can pass through the control surface promoting agent (PVB, PVA, SDS, CTAB, Brij-X) add-on and kind are controlled.At room temperature, deposition voltage is 2～100V/cm, and depositing time is 0.2～60 minute, deposits surfacing at last on cathode substrate, be uniformly dispersed, and the titanium dioxide nano material film that aperture, porosity, thickness are all controlled, its technological process is:
Tensio-active agent (dispersion agent, pore-forming material) is put into dehydrated alcohol, and ultrasonic 20～60min fully dissolves tensio-active agent, and then with titanium dioxide nano material, (0.1～8wt%) puts into solution respectively to the metallic salt ionogen, and ultrasonic agitation is even.Doing anode with stainless steel, nickel sheet, aluminium flake, platinized platinum, conductive glass, conducting high polymers thing etc., is negative electrode with cleaned electrically conducting transparent substrate.Negative electrode and anode spacing are from being 0.3～3 centimetre, and constant voltage power supply is as electric supply installation, and deposition voltage is 2～100V/cm, and depositing time is 0.2～60 minute.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the titanium dioxide nano material film of 1～20 μ m.This film is handled 1～3h through 400 ℃～550 ℃ thermal treatments or low-temperature microwave again, obtains final titanium dioxide nano material film.
With the light anode of above-mentioned titanium dioxide nano material film, and be assembled into liquid state and all-solid-state dye-sensitized solar cell as dye sensitization solar battery.The structure of this solar cell is a laminate structure, that is: at the surperficial electrophoretic deposition titanium dioxide nano material film of conductive substrates (1) (2), around titanium dioxide nano material, dyestuff sensitizing layer (3) is arranged, under dye coating (3), charge into ionogen (4), have the platinum plating counter electrode at ionogen (4).
Embodiment 1:
The 0.5wt%PVB tensio-active agent is put into dehydrated alcohol, and ultrasonic 30min fully dissolves tensio-active agent, then with the TiOx nano crystalline substance (median size 25nm) of 5wt%, and 0.8wt%Ti (SO 4) 2Ionogen is put into solution successively, and ultrasonic agitation is even.Doing anode with stainless steel, is negative electrode with cleaned transparent ITO conductive glass.Constant voltage power supply is as electric supply installation, and deposition voltage is 5V/cm, and depositing time is 30 minutes.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the brilliant film of the TiOx nano of 9.2 μ m.This film obtains the brilliant film of final TiOx nano again through 500 ℃ of thermal treatment 2h.Be assembled into dye sensitization solar battery with the brilliant film of this TiOx nano, dyestuff is many pyridines of carboxylic acid ruthenium, and ionogen is I 2The second cyanogen solution of+LiI+TBP (four tertiary butyl pyridines) has obtained 4.1% photoelectric transformation efficiency.
Embodiment 2:
The 1wt%PVA tensio-active agent is put into dehydrated alcohol, and ultrasonic 30min fully dissolves tensio-active agent, then with the titanium oxide nanotubes (mean outside diameter 10nm, internal diameter 5nm) of 10wt%, and 2wt%Zn (NO 3) 2Ionogen is put into solution successively, and ultrasonic agitation is even.Doing anode with stainless steel, is negative electrode with cleaned transparent FTO conductive glass.Constant voltage power supply is as electric supply installation, and deposition voltage is 20V/cm, and depositing time is 20 minutes.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the titanium oxide nanotubes film of 12 μ m.This film obtains final titanium oxide nanotubes film again through 450 ℃ of thermal treatment 2h.Be assembled into dye sensitization solar battery with this titanium oxide nanotubes film, dyestuff is many pyridines of carboxylic acid ruthenium, and ionogen is I 2The 1 methyl dipropyl imidazole ion liquid solution of+LiI+TBP (four tertiary butyl pyridines) has obtained 7.8% photoelectric transformation efficiency.
Embodiment 3:
The 3wt%SDS tensio-active agent is put into dehydrated alcohol, and ultrasonic 30min fully dissolves tensio-active agent, then with the TiOx nano rod (mean outside diameter 15nm) of 15wt%, and 4wt%Ni (NO 3) 2Ionogen is put into solution successively, and ultrasonic agitation is even.Doing anode with stainless steel, is negative electrode with cleaned transparent flexible ITO polymkeric substance.Constant voltage power supply is as electric supply installation, and deposition voltage is 40V/cm, and depositing time is 10 minutes.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the TiOx nano rod film of 10.5 μ m.This film obtains final TiOx nano rod film again through microwave treatment 1h.Be assembled into dye sensitization solar battery with this TiOx nano rod film, dyestuff is many pyridines of carboxylic acid ruthenium, and ionogen is I 2The second cyanogen solution of+LiI+TBP (four tertiary butyl pyridines) has obtained 2.3% photoelectric transformation efficiency.
Embodiment 4:
The 4wt%CTAB tensio-active agent is put into dehydrated alcohol, and ultrasonic 30min fully dissolves tensio-active agent, then with the TiOx nano crystalline substance (median size 25nm) of 30wt%, and 6wt%, Al (NO 3) 3Ionogen is put into solution successively, and ultrasonic agitation is even.Doing anode with stainless steel, is negative electrode with cleaned transparent ITO conductive glass.Constant voltage power supply is as electric supply installation, and deposition voltage is 80V/cm, and depositing time is 4 minutes.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the brilliant film of the TiOx nano of 8.7 μ m.This film obtains the brilliant film of final TiOx nano again through microwave treatment 3h.Be assembled into dye sensitization solar battery with the brilliant film of this TiOx nano, dyestuff is many pyridines of carboxylic acid ruthenium, and ionogen is I 2The second cyanogen solution of+LiI+TBP (four tertiary butyl pyridines) has obtained 6.5% photoelectric transformation efficiency.
Embodiment 5:
The 6wt%Brij56 tensio-active agent is put into dehydrated alcohol, and ultrasonic 30min fully dissolves tensio-active agent, then with the TiOx nano rod (mean outside diameter 15nm) of 40wt%, and 8wt%ZnCl 2Ionogen is put into solution successively, and ultrasonic agitation is even.Doing anode with stainless steel, is negative electrode with cleaned transparent FTO conductive polymers.Constant voltage power supply is as electric supply installation, and deposition voltage is 100V/cm, and depositing time is 0.3 minute.Obtain surfacing at last on cathode substrate, be uniformly dispersed, thickness is the TiOx nano rod film of 13.6 μ m.This film obtains final TiOx nano rod film again through 550 ℃ of thermal treatment 2h.Be assembled into dye sensitization solar battery with this TiOx nano rod film, dyestuff is many pyridines of carboxylic acid ruthenium, and ionogen is I 2The second cyanogen solution of+LiI+TBP (four tertiary butyl pyridines) has obtained 3.1% photoelectric transformation efficiency.

Claims (4)

1、一种氧化钛纳米材料薄膜及其制备方法，采用电泳沉积法，其特征在于：所述方法是将氧化钛纳米材料粉体、表面活性剂、无水乙醇均匀混合后，用金属盐类做电解质，经超声分散，充分搅拌后获得分散、均匀、稳定的氧化钛纳米材料悬浮液；以沉积衬底阳极不锈钢、镍片、铝片、铂片、导电玻璃、导电高分子聚合物做阳极，透明ITO导电玻璃、透明FTO导电玻璃、透明柔性ITO聚合物，透明FTO导电聚合物作为沉积阴极，恒压电源作为供电装置。室在室温下，沉积电压为2～100V/cm，沉积时间为0.2～60分钟，最后在阴极衬底上沉积出表面平整，分散均匀，孔径、孔隙率、厚度均可控的氧化钛纳米材料薄膜。该薄膜再经400℃～550℃热处理或低温微波处理1～3h，获得最终的氧化钛纳米材料薄膜；其工艺过程为：1. A titanium oxide nanomaterial thin film and a preparation method thereof, which adopt electrophoretic deposition, are characterized in that: the method is to uniformly mix titanium oxide nanomaterial powder, surfactant and dehydrated alcohol, and then use metal salts to As an electrolyte, after ultrasonic dispersion and sufficient stirring, a dispersed, uniform and stable titanium oxide nanomaterial suspension is obtained; the deposition substrate anode stainless steel, nickel sheet, aluminum sheet, platinum sheet, conductive glass, and conductive polymer are used as anodes , Transparent ITO conductive glass, transparent FTO conductive glass, transparent flexible ITO polymer, transparent FTO conductive polymer as deposition cathode, constant voltage power supply as power supply device. The chamber is at room temperature, the deposition voltage is 2-100V/cm, and the deposition time is 0.2-60 minutes. Finally, titanium oxide nanomaterials with smooth surface, uniform dispersion, and controllable pore size, porosity, and thickness are deposited on the cathode substrate. film. The film is then subjected to heat treatment at 400°C-550°C or low-temperature microwave treatment for 1-3 hours to obtain the final titanium oxide nanomaterial film; the process is as follows: (1)将表面活性剂放入无水乙醇中，超声，使表面活性剂充分溶解，所述表面活性剂的加入量为0.1～6wt％；(1) putting the surfactant into absolute ethanol, and ultrasonically dissolving the surfactant fully, and the addition of the surfactant is 0.1 to 6wt%; (2)将体积分数为5～40％的氧化钛纳米材料和0.1～8wt％金属盐类电解质分别放入溶液中，超声搅拌均匀；(2) putting titanium oxide nanomaterials with a volume fraction of 5-40% and metal salt electrolytes with a volume fraction of 0.1-8wt% into the solution, and ultrasonically stirring them evenly; (3)以不锈钢、镍片、铝片、铂片、导电玻璃、导电高分子聚合物做阳极，以清洗好的透明导电衬底为阴极，阴极和阳极间距离为0.3～3厘米，恒压电源作为供电装置，沉积电压为2～100V/cm，沉积时间为0.2～60分钟，在阴极衬底上获得表面平整，分散均匀，厚度为1～20μm的氧化钛薄膜。(3) Use stainless steel, nickel sheet, aluminum sheet, platinum sheet, conductive glass, and conductive polymer as the anode, and use the cleaned transparent conductive substrate as the cathode. The distance between the cathode and the anode is 0.3 to 3 cm. The power supply is used as a power supply device, the deposition voltage is 2-100V/cm, the deposition time is 0.2-60 minutes, and a titanium oxide film with a flat surface, uniform dispersion and a thickness of 1-20 μm is obtained on the cathode substrate. (4)将步骤3的薄膜再经400℃～550℃热处理或低温微波处理1～3h，获得最终的氧化钛纳米材料薄膜。(4) The film in step 3 is subjected to heat treatment at 400° C. to 550° C. or low-temperature microwave treatment for 1 to 3 hours to obtain the final titanium oxide nanomaterial film. 2、根据权利要求1所述的制备方法，其特征在于：所述反应原料中氧化钛纳米材料为氧化钛纳米晶，氧化钛纳米管，氧化钛纳米线。2. The preparation method according to claim 1, characterized in that: the titanium oxide nanomaterials in the reaction raw materials are titanium oxide nanocrystals, titanium oxide nanotubes, and titanium oxide nanowires. 3、根据权利要求1所述的制备方法，其特征在于：所述的表面活性剂为聚乙烯醇缩丁醛，聚乙烯醇，十二烷基硫酸钠，十六烷基三甲基溴化胺，聚氧乙烯醚类各种阴离子，阳离子，非极性表面活性剂。3. The preparation method according to claim 1, characterized in that: said surfactant is polyvinyl butyral, polyvinyl alcohol, sodium lauryl sulfate, cetyl trimethyl bromide Amines, polyoxyethylene ethers, various anionic, cationic, non-polar surfactants. 4、根据权利要求1所述的制备方法，其特征在于：所述的金属盐类电解质为Ti(SO4)2，Zn(NO3)2，Ni(NO3)2，Al(NO3)3，ZnCl2各种金属盐类。4. The preparation method according to claim 1, characterized in that: the metal salt electrolyte is Ti(SO 4 ) 2 , Zn(NO 3 ) 2 , Ni(NO 3 ) 2 , Al(NO 3 ) 3 , ZnCl 2 various metal salts.
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