CN101976611B - TiO2 nanowire array film light anode and preparation method thereof - Google Patents

TiO2 nanowire array film light anode and preparation method thereof Download PDF

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CN101976611B
CN101976611B CN 201010264000 CN201010264000A CN101976611B CN 101976611 B CN101976611 B CN 101976611B CN 201010264000 CN201010264000 CN 201010264000 CN 201010264000 A CN201010264000 A CN 201010264000A CN 101976611 B CN101976611 B CN 101976611B
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nano
array film
tio
wire array
light anode
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CN101976611A (en
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魏爱香
葛增娴
刘俊
赵旺
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Guangdong University of Technology
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Guangdong University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a TiO2 nanowire array film light anode and a preparation method thereof. The structure of the light anode comprises common glass, an F-doped SnO2 transparent conducting film and a TiO2 nanowire array film. The preparation method comprises the following step of directly synthesizing the TiO2 nanowire array film which is used as a light anode of a dye-sensitization solar battery on a FTO (Tin Oxide) glass substrate by using the mixture of concentrated hydrochloric acid, deionized water and tetrabutyl titanate as a reaction precursor in a hydrothermal synthesis technique. The method controls the diameters and densities of nanowires by changing the ratio of the concentrated hydrochloric acid to the deionized water in the reaction precursor and the concentration of the tetrabutyl titanate, controls the lengths of the TiO2 nanowires by changing reaction time, and ensures that the electrode has higher light capturing efficiency, improves the transporting capacity of photon-generated carriers and reduces the compounding process of the photon-generated carrier by utilizing higher light utilization rate and favorable electron shifting properties of the TiO2 nanowires, thereby improving the photoelectric conversion efficiency of the dye-sensitization solar battery.

Description

TiO 2Nano-wire array film light anode and preparation method thereof
Technical field
The present invention relates to a kind of TiO 2Nano-wire array film light anode and preparation method thereof.
Background technology
TiO 2Nano structural material has a wide range of applications at aspects such as DSSC, opto-electronic device, photochemical catalyst, transducers; Be that social development has the research object of material impact to the future economy in the current nano materials research field, it carried out controlledly synthesis have profound significance.Along with going deep into of research work; People more and more stress controllability to the research of nano material, and this not only requires to prepare has desirable crystal structure, chemical composition, pattern and size, and can various nanostructures organically be assembled; The controlled construction package that is built into various complicacies; Make it have nano material unique machinery, electricity, optics and chemical property, have only and to realize better controlled, could be nano-TiO some particular configuration or character 2Some peculiar performance finally reach industrialization and provide safeguard.
With TiO 2Research as the DSSC (DSSC) of light anode has received extensive concern.The light anode of traditional DSSC generally adopts nano-TiO 2Porous membrane, TiO 2Though porous membrane is absorbing dye fully, light induced electron receives the influence that discharges with heat of catching of particle surface defect state energy level in transmission course, the electron recombination rate is increased, and diffusion coefficient reduces, and has limited the conversion efficiency of battery.And one-dimensional nano structure such as nano wire, nanotube etc. can provide the path of direct light induced electron, improve electron diffusion length, reduce the compound of electronics, increase electron lifetime, and then improve the efficient of the opto-electronic conversion of battery.Therefore, the direct (SnO that mixes F that is coated with on glass on the transparent conducting glass substrate 2Conductive film is called for short FTO) synthetic TiO 2Nano-wire array film is to realize that it is applied to the key technology of DSSC.
Summary of the invention
The purpose of this invention is to provide a kind of TiO 2Nano-wire array film light anode and preparation method thereof.
A kind of TiO provided by the invention 2Nano-wire array film light anode, its structure by simple glass, mix the SnO of F 2Nesa coating (FTO) and TiO 2Nano-wire array film is formed; The 1st layer is simple glass, and the 2nd layer for mixing the SnO of F 2Nesa coating (FTO), the 3rd layer is the monocrystalline TiO of vertical FTO glass substrate growth 2Nano-wire array film.
A kind of TiO provided by the invention 2Nano-wire array film light anode preparation method may further comprise the steps:
1) hydro-thermal synthetic technology synthetic TiO on the FTO glass substrate 2Nano-wire array film;
2) the TiO for preparing 2Nano-wire array film is put into the Muffle furnace sintering, and (structural formula is (n-2Bu at ruthenium complex N719 dyestuff then 4N) 2-cis-Ru (L 1) 2(NCS) 2] ethanol solution in soak 24h, take out the dyestuff of back flush away remained on surface, dry, just obtain TiO 2Nano-wire array film light anode.
Above-mentioned steps 1) on the FTO glass substrate, prepares TiO in 2The method of nano-wire array film is: keeping cumulative volume is under the condition of 40mL, with concentrated hydrochloric acid and deionized water according to HCl: H 2O=15: 25 or the volume ratio of 20: 20 or 25: 15 or 26.7: 13.3 mix, magnetic stirrer 5 minutes splashes into the butyl titanate of 0.4～0.8mL again, stirs 7 minutes; It is the autoclave of 100mL that the solution for preparing is put into band teflon-lined volume; Keep the FTO glass substrate of the wide 1.5cm that cleans up, long 3.5～4cm conducting film to be placed in the agitated reactor towards having a down dip; The angle of glass and wall remains in 10～45 ° of scopes; Keep gap that FTO glass has 0.5cm simultaneously on solution, be used to connect test electrode; Seal still then, and put into drying box to agitated reactor and be heated to 120～180 ℃ and react, the reaction time is 4～20h; After reaction finishes, naturally cool to room temperature, take out FTO glass, with deionized water rinsing repeatedly, natural airing in air then.
Above-mentioned steps 2) in the TiO for preparing 2Nano-wire array film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to then about 80 ℃ to take out, and putting into concentration immediately is 5.0 * 10 -4Soak 24h in the ruthenium complex N719 dyestuff ethanol solution of mol/L.Take out the dyestuff of back, dry, obtain TiO with ethanol flush away remained on surface 2Nano-wire array film light anode.
The invention has the beneficial effects as follows:
Through the hydrochloric acid and the ratio of water, concentration, reaction time and the reaction temperature of butyl titanate in the change pre-reaction material, diameter, density and the length of control nano wire realize TiO 2The controllable growth of nano-wire array.
The TiO that on the FTO glass substrate, directly synthesizes 2Nano-wire array film can directly be used as dye-sensitized solar cell anode, utilizes TiO 2Light utilization efficiency that nano wire is higher and good electron transfer characteristic; Ensured that electrode has higher light capture rate; Improve the transport capability of photo-generated carrier, reduced the recombination process of photo-generated carrier, thereby improved the electricity conversion of DSSC.
Description of drawings
Fig. 1 is TiO 2The structural representation of nano-wire array film light anode.The 1st layer is simple glass, and the 2nd layer for mixing the SnO of F 2Nesa coating (FTO), the 3rd layer is the monocrystalline TiO of vertical FTO glass substrate growth 2Nano-wire array film.
Fig. 2, Fig. 3, Fig. 4 and Fig. 5 are butyl titanate 0.5mL, 150 ℃ of hydrothermal temperatures, and in 20 hours reaction time, concentrated hydrochloric acid and deionized water volume ratio were respectively 15: 25; 20: 20; 25: 15; 26.7: 13.3 o'clock (the cumulative volume 40mL that keeps the two), orthotropic TiO on the FTO glass substrate 2The SEM top view of nano-wire array film; Fig. 6 and Fig. 7 are respectively the volume ratios 20: 20 and 25: 15 o'clock of concentrated hydrochloric acid and deionized water, orthotropic TiO on the FTO glass substrate 2The SEM sectional view of nano-wire array film.
Embodiment
1. on the FTO glass substrate, prepare TiO 2Nano-wire array film.
Adopt the hydro-thermal synthetic technology of low temperature low energy consumption on the FTO glass substrate, to prepare TiO 2Nano-wire array film.Keeping cumulative volume is under the condition of 40mL, with concentrated hydrochloric acid and deionized water according to HCl: H 2O=15: 25,20: 20,25: 15,26.7: 13.3 volume ratio is mixed, and magnetic stirrer 5 minutes splashes into the butyl titanate of 0.4～0.8mL again, stirs 7 minutes.It is the autoclave of 100mL that the solution for preparing is put into band teflon-lined volume; Keep the FTO glass substrate of the wide 1.5cm that cleans up, long 3.5～4cm conducting film to be placed in the agitated reactor towards having a down dip; The angle of glass and wall remains in 10～45 ° of scopes; Keep FTO glass to have an appointment 0.5cm on solution simultaneously, be used to connect test electrode.Seal still then, and put into drying box to agitated reactor and be heated to 120-180 ℃ and react, the reaction time is 4-20h.After reaction finishes, naturally cool to room temperature, take out FTO glass, with deionized water rinsing repeatedly, natural airing in air then.
2.TiO 2The controllable growth of nano-wire array film.
Through changing concentrated hydrochloric acid and the ratio of deionized water and the concentration of butyl titanate in the reaction precursor body, can control the diameter and the density of nano wire; Through changing the reaction time, can control TiO 2The length of nano wire, thus realize TiO 2The controlledly synthesis of nano-wire array.
(1) amount of butyl titanate immobilizes in the reaction precursor body, and hydrochloric acid many grown nano wire diameter more is thin more, and the bar number density of nano wire is many more in the unit are.For example, butyl titanate 0.5mL, 150 ℃ of growth temperatures,, growth time 20h works as HCl: H 2O=15: 25,20: 20,25: 15,26.7: 13.3 o'clock, the diameter of nano wire was respectively 230,110, and 30 and 10nm.But, if hydrochloric acid continue to increase, example hydrochloric acid 30mL, during deionized water 10mL, the nano wire of grow not go out on the FTO substrate, if instead hydrochloric acid is very little, butyl titanate is hydrolyzed into white powder immediately and is deposited in bottom the solution, can not the FTO substrate on grow nanowire.
When (2) concentrated hydrochloric acid and deionized water ratio and cumulative volume remained unchanged in the reaction precursor body, the amount of butyl titanate was big more, and the grown nano wire diameter is thick more, and the bar number density of nano wire is more little in the unit are.For example, when keeping 150 ℃ of hydrothermal temperatures, 20 hours reaction time, hydrochloric acid 20mL, under the constant condition of deionized water 20mL, when butyl titanate was increased to 0.8mL gradually from 0.4mL, the diameter of nano wire was increased to 210nm from 100nm, and density is from 24/μ m 2Reduce to 13/μ m 2
(3) the hydro-thermal reaction time mainly influences the length of nano wire, the reaction incipient stage, and the nanowire growth rapid speed, the speed of growth slows down then, and the length of last nano wire is not just changing in time.For example, 150 ℃ of hydrothermal temperatures, hydrochloric acid 20mL, deionized water 20mL, under the condition of butyl titanate 0.5mL, growth time 4,8,12,16 is respectively 1.5,2.6,3.1,4.1 and 4.1 μ m with the length of the nano wire of 20h correspondence.
(4) before the hydro-thermal reaction, in concentration the TiCl of 0.1mol/L FTO glass 4After soaking 30min under 80 ℃ in the aqueous solution, the fine and close TiO of the one deck of can on FTO, growing 2Film, and then carry out hydro-thermal reaction and prepare TiO 2Nano wire, under the same conditions, TiO 2It is thinner that nano wire can be grown.TiCl 4The compound method of the aqueous solution is to put 100ml water earlier to be put into and to form ice cube in the refrigerator, and then splashes into an amount of TiCl 4Making its concentration is 0.1mol/L, then ice-out, puts into FTO solution and under 80 ℃ of constant temperature, soaks 30min.
(5) partly replace deionized water with toluene, also can make TiO 2The variation in diameter of nano wire.
3. with TiO 2The assembling of the DSSC of nano-wire array film light anode.
The TiO for preparing 2Nano-wire array film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to then about 80 ℃ to take out, and putting into concentration immediately is 5.0 * 10 -4(structural formula is (n-2Bu to the ruthenium complex N719 dyestuff of mol/L 4N) 2-cis-Ru (L 1) 2(NCS) 2] ethanol solution in soak 24h, take out the dyestuff of back with ethanol flush away remained on surface, dry, be exactly prepared light anode, keep in Dark Place.Then with the FTO glass that is coated with the Pt film to electrode, KI/I 2Solution be electrolyte [0.5mol/L KI+0.05mol/L I 2Solvent: acetonitrile (volume integral 80)+isopropyl alcohol (volume fraction 20)], be assembled into battery.

Claims (2)

1. TiO 2The preparation method of nano-wire array film light anode is characterized in that may further comprise the steps:
1) keeping cumulative volume is under the condition of 40mL, with concentrated hydrochloric acid and deionized water according to HCl: H 2O=15: 25 or the volume ratio of 20: 20 or 25: 15 or 26.7: 13.3 mix, magnetic stirrer 5 minutes splashes into the butyl titanate of 0.4～0.8mL again, stirs 7 minutes; It is the autoclave of 100mL that the solution for preparing is put into band teflon-lined volume; Keep the FTO glass substrate of the wide 1.5cm that cleans up, long 3.5～4cm conducting film to be placed in the agitated reactor towards having a down dip; The angle of glass and wall remains in 10～45 ° of scopes; Keep gap that FTO glass has 0.5cm simultaneously on solution, be used to connect test electrode; Seal still then, and put into drying box to agitated reactor and be heated to 120～180 ℃ and react, the reaction time is 4～20h; Reaction naturally cools to room temperature after finishing, and takes out FTO glass, and with deionized water rinsing repeatedly, natural airing in air is accomplished directly synthetic TiO on the FTO glass substrate then 2Nano-wire array film;
2) the TiO for preparing 2Nano-wire array film is put into the Muffle furnace sintering, is (n-2Bu at its structural formula of ruthenium complex N719 dyestuff then 4N) 2-cis-Ru (L 1) 2(NCS) 2Ethanol solution in soak 24h, take out the dyestuff of back flush away remained on surface, dry, just obtain TiO 2Nano-wire array film light anode.
2. preparation method according to claim 1 is characterized in that above-mentioned steps 2) in the TiO for preparing 2Nano-wire array film is put into 450 ℃ of sintering 30min of Muffle furnace, cools to then about 80 ℃ to take out, and putting into concentration immediately is 5.0 * 10 -4Soak 24h in the ruthenium complex N719 dyestuff ethanol solution of mol/L; Take out the dyestuff of back, dry, obtain TiO with ethanol flush away remained on surface 2Nano-wire array film light anode.
CN 201010264000 2010-08-25 2010-08-25 TiO2 nanowire array film light anode and preparation method thereof Expired - Fee Related CN101976611B (en)

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