CN103280323A - Tin-doped dye-sensitized TiO2 nanocrystal film photoelectrode and preparation method and applications thereof - Google Patents

Tin-doped dye-sensitized TiO2 nanocrystal film photoelectrode and preparation method and applications thereof Download PDF

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CN103280323A
CN103280323A CN2013101684742A CN201310168474A CN103280323A CN 103280323 A CN103280323 A CN 103280323A CN 2013101684742 A CN2013101684742 A CN 2013101684742A CN 201310168474 A CN201310168474 A CN 201310168474A CN 103280323 A CN103280323 A CN 103280323A
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tin
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optoelectronic pole
titanium
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段彦栋
傅年庆
方艳艳
周晓文
林原
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Institute of Chemistry CAS
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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
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    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a tin-doped dye-sensitized TiO2 nanocrystal film photoelectrode and a preparation method and applications thereof. The film photoelectrode is a nanocrystal film photoelectrode with a porous structure which is formed after a tin-doped TiO2 nanocrystal particle colloid is coated on a conductive substrate and is subjected to thermal treatment. On one hand, after tin is doped, the quantity of charge carriers is increased, the electronic transmission performance of a TiO2 film is obviously increased, and a TiO2energy band structure can be changed so that the photovoltage is increased. The preparation method is simple, is easy to operate, and is especially suitable for the industrial production preparation of the dye-sensitized TiO2 nanocrystal film photoelectrode.

Description

Tin dope dye sensitization TiO 2Nano-crystalline film photoelectric electrode and preparation method thereof and application
Technical field
The present invention relates to a kind of tin dope dye-sensitized solar cells (DSSCs) TiO 2Nano-crystalline film photoelectric electrode and preparation method thereof and application.
Background technology
In the preparation technology of DSSCs, the semiconductor (TiO of nanostructure 2) porous surface structure (specific surface, roughness, thickness etc.) of electrode affects the photoelectric properties of battery consumingly, so the optimization of thin film preparation process seems particularly important.Domestic and international research group all attempts by nanocrystalline porous film being carried out the opto-electronic conversion performance that optimization processes such as physics, chemistry improve DSSCs at present.This is comprising using TiCl 4Handle porous film electrode with acid etc., improve the transmission performance of electronics in nanocrystalline porous film; By with transition metal, rare earth element that catalytic performance is arranged etc. to TiO 2Film mixes, and changes TiO 2Fermi level, impurity energy level and deep energy level structure in the film suppress the compound of electron-hole pair, improve transmission and the transfer performance of electronics, thereby improve the photoelectric properties of DSSCs.
At present the metal-doped technology of report can only be from improving the performance of DSSCs on the one hand, as improve its short-circuit photocurrent (as doping Nb etc.), or improve its open circuit photovoltage (as doping Ta).
Summary of the invention
The purpose of this invention is to provide a kind of tin dope dye-sensitized solar cells (DSSCs) TiO 2Nano-crystalline film photoelectric electrode and preparation method thereof and application.
The method for preparing optoelectronic pole provided by the invention comprises the steps:
1) titanium salt and sn-containing compound are dissolved in solvent respectively after mixing be hydrolyzed successively and hydro-thermal reaction, again with gained colloidal solution evaporate to dryness, obtain the TiO of doped tin 2Colloid;
2) with the TiO of step 1) gained doped tin 2Colloid evenly is coated on the electro-conductive glass, obtains the TiO of doped tin after the heat treatment 2Membrane electrode;
3) with step 2) TiO of gained doped tin 2After the membrane electrode drying, immerse in the solution of dyestuff, taking-up is dried, and obtains described optoelectronic pole.
In the described step 1) of said method, titanium salt is selected from least a in isopropyl oxygen alcohol titanium, butyl titanate, tetraisopropyl titanate, metatitanic acid four own esters and the titanium tetrachloride;
Described sn-containing compound is selected from least a in butter of tin, stannous chloride and the tert-butoxy tin;
Described solvent is selected from least a in n-butanol, isopropyl alcohol, absolute ethyl alcohol and the water;
Tin element in the described sn-containing compound and the mol ratio of the titanium elements in the titanium salt are 0.25-1: 100, be specially 0.25: 100,0.5: 100,0.75: 100,1: 100, (0.5-1): 100;
The volume ratio of described titanium salt and solvent is 5-50: 100, be specially 10: 100,13: 100,17: 100,25: 100,33: 100, (10-33): 100 or (13-25): 100;
In the described hydrolysing step, temperature is 20-100 ℃, is specially 25 ℃ or 35 ℃ or 40 ℃ or 60 ℃ or 25-60 ℃; Time is 1-10 hour, is specially 1.5 hours or 3 hours or 4 hours or 4.5 hours or 1.5-4.5 hour; In the described hydro-thermal reaction step, temperature is 150-240 ℃, is specially 180 ℃ or 200 ℃, and the time is 4-24 hour, is specially 6,8,12 or 16 hours;
The TiO of described doped tin 2In the colloid, solid content (also being the quality percentage composition of solid content in the gained colloid) is 5-30%, is specially 13%.
Described step 2) in, the material that constitutes described electro-conductive glass is selected from least a in FTO, ITO and the titanium;
In the heat treatment step, temperature is 300-600 ℃, is specially 450 ℃, and the time is 10-60 minute, is specially 30 minutes.
In the solution of described step 3) dyestuff, dyestuff be selected from N3 (also namely 4,4 '-the dicarboxylic acids bipyridyl ruthenium (along two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) close ruthenium (II))), at least a in phthalocyanine and the porphyrin;
Wherein, the structural formula of N3 is as follows:
Figure BDA00003146191300021
Solvent is selected from least a in isopropyl alcohol, n-butanol and the absolute ethyl alcohol;
The concentration of solution is 2 * 10 -4-8 * 10 -4M is specially 5 * 10 -4M;
The optoelectronic pole that the method that the invention described above provides prepares also belongs to protection scope of the present invention.Wherein, described optoelectronic pole is from the bottom to top successively by described electro-conductive glass, TiO 2Membrane electrode layer and dye coating are formed.The material that constitutes described electro-conductive glass is selected from least a in FTO, ITO and the titanium;
Described TiO 2The thickness of membrane electrode layer is 8-12 μ m;
The dyestuff adsorbance of described dye coating is 1 * 10 -7-5 * 10 -7Mol cm -2, be specially 1.32 * 10 -7Mol cm -2
The dyestuff that constitutes described dyestuff is selected from least a in N3, phthalocyanine and the porphyrin.
The optoelectronic pole that the invention described above provides preparation in the DSSC application and contain the DSSC of described optoelectronic pole, also belong to protection scope of the present invention.Wherein, described dyestuff is selected from least a in N3, phthalocyanine and the porphyrin.
Film photoelectric electrode provided by the invention is the TiO by doping metals 2Receive brilliant particle colloid in the conductive substrates coating and heat-treat the loose structure nano-crystalline film photoelectric electrode that the back forms.On the one hand, behind the tin dope, thereby the quantity that has not only increased charge carrier has obviously improved conductance, and can change TiO 2The position that can be with and then raising photovoltage, this loose structure nano-crystal thin-film has high conductivity and the preparation method is simple, and easy operating is specially adapted to dye sensitization TiO 2The suitability for industrialized production preparation of nano-crystalline film photoelectric electrode, thereby expanded dye sensitization TiO greatly 2The application prospect of nano-crystal thin-film solar cell.The dye sensitization TiO of the doping metals of the present invention's preparation 2The photoelectric properties excellence of nano-crystalline film photoelectric electrode has high density of photocurrent 16.01mAcm -2, high open circuit photovoltage 722mV and high-photoelectric transformation efficiency 8.31% are specially adapted to use as work electrode in the dye sensitization nano-crystal thin-film solar cell.
Description of drawings
Fig. 1 is the ESEM picture on gained optoelectronic pole surface.
Fig. 2 is the ESEM picture of optoelectronic pole cross section.
Fig. 3 is the absorption spectrum of dyestuff desorption liquid.
Fig. 4 is that the x-ray photoelectron spectroscopy of optoelectronic pole structure characterizes.
Fig. 5 is the photoelectric properties curve of the DSSC of doped tin.
Fig. 6 is TiO 2The nano-crystalline film photoelectric electrode structure chart.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.
Before enumerating embodiment, earlier the method for all using among each embodiment with general character is done to describe, then will be no longer in each embodiment the method for these general character be repeated in this description.
The coating method of colloid: the both sides of the conductive substrates that cleans up are fixed with adhesive tape, dipped in glass bar and take a morsel colloid and it is coated onto on the conductive substrates preparation TiO equably 2Nano-crystalline film photoelectric electrode.Control TiO with the thickness of adhesive tape and the number of times that repeats to apply when filming 2The thickness of nano-crystalline film photoelectric electrode.
The dye sensitization TiO of doped tin provided by the invention 2The preparation method of nano-crystalline film photoelectric electrode comprises: with the TiO that coats 2Membrane electrode dries in air naturally, puts into 450 ℃ of heat treatments of Muffle furnace 30 minutes again, the TiO that obtains 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5x10 -44,4 of M '-dicarboxylic acids bipyridyl ruthenium (along two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) dowel (II)) ethanolic solution in, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode.
Method of measurement: with the dye sensitization TiO of embodiment gained doped tin 2Nano-crystalline film photoelectric electrode uses the platinized platinum conduct to electrode as work electrode.With containing 0.5M LiI, 0.05MI 2With the trimethoxy propionitrile solution of 0.5M four tertiary butyl pyridines as electrolyte, be assembled into DSSC and carry out performance measurement.The digital source table (Keithley2611) that the photoelectric properties of battery are computerizedd control is at room temperature measured.Light source uses solar simulator (Newport, Oriel, 91160-1000) incident intensity 100mW/cm 2, illuminating area 0.2cm 2Except as otherwise noted, the measurement of photoelectric properties of the present invention all is to carry out under room temperature (25 ℃).
Embodiment 1
(1) be to be hybridly prepared into titanium salt solution at 1: 6 with titanium salt titanium tetrachloride and solvent isopropyl alcohol with volume ratio, tin source stannous chloride and solvent isopropyl alcohol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 40 ℃ of reactions 3 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 0.5: 100;
After the reaction, mixed liquor put under 240 ℃ of the autoclaves carried out hydro-thermal reaction 6 hours; Colloidal solution after the end is rotated evaporation, until obtaining the TiO that solid content is 13% doped tin 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the clean conductive glass FTO, is to heat-treat under 450 ℃ to make the TiO that thickness is 12 μ m in 30 minutes in temperature then 2Membrane electrode.
(3) TiO that step (2) is obtained 2Membrane electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
The structure of this optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass (numbering 1 in the corresponding diagram 6), thickness as shown in Figure 6 from the bottom to top successively 2Membrane electrode layer (numbering 2 in the corresponding diagram 6) and be adsorbed on TiO 2The surface the N3 dye coating form that (adsorbance is 1.32 * 10 -7Mol cm -2) form.
Fig. 1 is the ESEM picture on this embodiment gained optoelectronic pole surface, as seen from the figure, and TiO 2Membrane electrode is loose structure.
Fig. 2 is the cross-sectional scans Electronic Speculum picture of this embodiment gained optoelectronic pole, as seen from the figure, and TiO 2The thickness of membrane electrode layer is 12 μ m.
The desorption of dyestuff: the TiO that has adsorbed dyestuff 2Membrane electrode is at 5mL0.05mol L -1The NaOH aqueous solution in soaked several minutes.Treat namely to get behind the complete desorption of dyestuff the desorption liquid of dyestuff, measure this dyestuff desorption liquid in the absorbance at 520nm wavelength place with ultraviolet-visible spectrophotometer.
Calculate the dyestuff adsorbance of membrane electrode by the absorption spectrum of measuring desorption liquid, computing formula is as follows:
C = A ϵ 520 S 0
Wherein, C is dyestuff adsorbance (mol cm -2);
A is the absorbance at 520nm place at wavelength for the NaOH solution of the N3 dyestuff that the work electrode desorption gets off;
S 0Geometric area (cm for the membrane electrode absorbing dye that is coated with colloid 2);
ε is wavelength when being 520nm, is adsorbed on the molar extinction coefficient of the N3 dye molecule of working electrode surface, is 1.42 * 10 4L mol -1Cm -1
Fig. 3 is the absorption spectrum of dyestuff desorption liquid, and as seen from the figure, the absorbance of dyestuff at the 520nm place is 0.438.By TiO 2The area of membrane electrode is 1cm * 1cm, and it is 1.32 * 10 that calculating can get the dyestuff adsorbance -7Mol cm -2
Fig. 4 is that the x-ray photoelectron spectroscopy of this embodiment gained optoelectronic pole film characterizes, and as seen from the figure, the content mol ratio of the content of Sn and Ti is 0.45: 100 in the film.
Fig. 5 makes the photoelectric properties curve of DSSC for this embodiment gained optoelectronic pole.As seen from the figure, the short-circuit photocurrent of DSSC is 16.01mA cm 2, the open circuit photovoltage is 722mV, and fill factor, curve factor is 0.71, and photoelectric conversion efficiency has reached 8.31%.
Embodiment 2
(1) be to be hybridly prepared into titanium salt solution at 1: 6 with titanium salt butyl titanate and solvent, n-butanol with volume ratio, tin source tert-butoxy tin, solvent, n-butanol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 25 ℃ of reactions 1.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin element in the tin source and the titanium salt mol ratio of titanium elements be 0.25: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 150 ℃ in temperature, and the reaction time is 24 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, until obtaining the TiO that solid content is 13% doped tin 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make the TiO that thickness is the doped tin of 12 μ m in 30 minutes in temperature then 2Membrane electrode.
(3) TiO of the doped tin that step (2) is obtained 2Membrane electrode is heat drying 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 3
(1) be to be hybridly prepared into titanium salt solution at 1: 6 with titanium salt isopropyl oxygen alcohol titanium and solvent, n-butanol with volume ratio, tin source tert-butoxy tin and solvent, n-butanol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 25 ℃ of reactions 1.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 1: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 240 ℃ in temperature, and the reaction time is 24 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make the TiO that thickness is 8 μ m in 30 minutes in temperature then 2Membrane electrode.
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 4
(1) be to be hybridly prepared into titanium salt solution at 1: 3 with titanium salt tetraisopropyl titanate and solvent, n-butanol with volume ratio, tin source butter of tin and solvent, n-butanol are hybridly prepared into tin source solution: then titanium salt solution and tin source solution are mixed in 25 ℃ of reactions 1.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 0.5: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 180 ℃ in temperature, and the reaction time is 6 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make the TiO that thickness is 8 μ m in 30 minutes in temperature then 2Membrane electrode.
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 5
(1) be to be hybridly prepared into titanium salt solution at 1: 8 with titanium salt metatitanic acid four own esters and solvent, n-butanol with volume ratio, tin source butter of tin and solvent, n-butanol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 40 ℃ of reactions 4 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 0.75: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 200 ℃ in temperature, and the reaction time is 8 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make the TiO that thickness is 10 μ m in 30 minutes in temperature then 2Membrane electrode.
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This this optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 6
(1) be to be hybridly prepared into titanium salt solution at 1: 6 with titanium salt isopropyl oxygen alcohol titanium and solvent isopropyl alcohol with volume ratio, tin source stannous chloride and solvent isopropyl alcohol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 60 ℃ of reactions 1.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 0.5: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 200 ℃ in temperature, and the reaction time is 16 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make TiO in 30 minutes in temperature then 2Membrane electrode:
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 7
(1) be to be hybridly prepared into titanium salt solution at 1: 4 with titanium salt butyl titanate and solvent absolute ethyl alcohol with volume ratio, tin source tert-butoxy tin and solvent absolute ethyl alcohol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 60 ℃ of reactions 1.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 1: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 180 ℃ in temperature, and the reaction time is 16 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make TiO in 30 minutes in temperature then 2Membrane electrode:
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.
Embodiment 8
(1) be to be hybridly prepared into titanium salt solution at 1: 10 with titanium salt tetraisopropyl titanate and solvent absolute ethyl alcohol with volume ratio, tin source tert-butoxy tin and solvent absolute ethyl alcohol are hybridly prepared into tin source solution, then titanium salt solution and tin source solution are mixed in 35 ℃ of reactions 4.5 hours that are hydrolyzed, wherein, in the mixed liquor in the tin in the tin source and the titanium salt mol ratio of titanium be 0.25: 100;
After the reaction, mixed liquor being put into autoclave, is to carry out hydro-thermal reaction under 240 ℃ in temperature, and the reaction time is 12 hours; Colloidal solution after hydro-thermal reaction finished is rotated evaporation, is the TiO of 13% doped tin until the solid content that obtains 2Colloid.
(2) TiO of the doped tin that step (1) is obtained 2The colloid of brilliant particle received evenly is coated on the conductive substrates that cleans up, and is to heat-treat under 450 ℃ to make TiO in 30 minutes in temperature then 2Membrane electrode.
(3) TiO that step (2) is obtained 2The nano-crystal thin-film electrode is heating 1 hour in 80 ℃ the baking oven in temperature, and subsequently electrode being immersed concentration is 5 * 10 -4In the ethanolic solution of the N3 of M, take out, with drying after the absolute ethyl alcohol flushing, namely make the dye sensitization TiO of doped tin 2Nano-crystalline film photoelectric electrode;
This optoelectronic pole is the TiO of 12 μ m by FTO electro-conductive glass, thickness from the bottom to top successively 2Membrane electrode layer and adsorbance are 1.32 * 10 -7Mol cm -2The N3 dye coating form.
The testing result of its photoelectric properties and embodiment 1 no substantive difference repeat no more.

Claims (10)

1. a method for preparing optoelectronic pole comprises the steps:
1) titanium salt and sn-containing compound are dissolved in solvent respectively after mixing be hydrolyzed successively and hydro-thermal reaction, again with gained colloidal solution evaporate to dryness, obtain the TiO of doped tin 2Colloid;
2) with the TiO of step 1) gained doped tin 2Colloid evenly is coated on the electro-conductive glass, obtains the TiO of doped tin after the heat treatment 2Membrane electrode;
3) with step 2) TiO of gained doped tin 2After the membrane electrode drying, immerse in the solution of dyestuff, taking-up is dried, and obtains described optoelectronic pole.
2. method according to claim 1 is characterized in that: in the described step 1), titanium salt is selected from least a in isopropyl oxygen alcohol titanium, butyl titanate, tetraisopropyl titanate, metatitanic acid four own esters and the titanium tetrachloride;
Described sn-containing compound is selected from least a in butter of tin, stannous chloride and the tert-butoxy tin;
Described solvent is selected from least a in n-butanol, isopropyl alcohol, absolute ethyl alcohol and the water;
Tin element in the described sn-containing compound and the mol ratio of the titanium elements in the titanium salt are 0.25-1: 100;
The volume ratio of described titanium salt and solvent is 5-50: 100, be specially 10: 100;
In the described hydrolysing step, temperature is 20-100 ℃, is specially 25 ℃; Time is 1-10 hour, is specially 1.5 hours;
In the described hydro-thermal reaction step, temperature is 150-240 ℃, and the time is 4-24 hour;
The TiO of described doped tin 2In the colloid, solid content is 5-30%, is specially 13%.
3. method according to claim 1 and 2 is characterized in that: described step 2), the material that constitutes described electro-conductive glass is selected from least a in FTO, ITO and the titanium;
Described step 2) in the heat treatment step, temperature is 300-600 ℃, is specially 450 ℃, and the time is 10-60 minute, is specially 30 minutes.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: in the solution of described step 3) dyestuff, dyestuff is selected from least a in N3, phthalocyanine and the porphyrin;
Solvent is selected from least a in isopropyl alcohol, n-butanol and the absolute ethyl alcohol;
The concentration of solution is 2 * 10 -4-8 * 10 -4M is specially 5 * 10 -4M;
In the described drying steps, temperature is 80-120 ℃, and the time is 1-5 hour.
5. the optoelectronic pole for preparing of the arbitrary described method of claim 1-4.
6. optoelectronic pole according to claim 5, it is characterized in that: described optoelectronic pole is from the bottom to top successively by described electro-conductive glass, TiO 2Thin layer and dye coating are formed.
7. optoelectronic pole according to claim 6 is characterized in that: described TiO 2The thickness of thin layer is 8-12 μ m;
The dyestuff adsorbance of described dye coating is 1 * 10 -7-5 * 10 -7Mol cm -2, be specially 1.32 * 10 -7Mol cm -2
8. the application of the arbitrary described optoelectronic pole of claim 5-7 in the preparation DSSC.
9. the DSSC that contains the arbitrary described optoelectronic pole of claim 5-7.
10. application according to claim 8 or 9 described batteries is characterized in that: described dyestuff is selected from least a in N3, phthalocyanine and the porphyrin.
CN2013101684742A 2013-05-06 2013-05-06 Tin-doped dye-sensitized TiO2 nanocrystal film photoelectrode and preparation method and applications thereof Pending CN103280323A (en)

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CN104701017A (en) * 2014-12-26 2015-06-10 北京大学深圳研究生院 Titanium dioxide film photo-electrode and preparation method and application thereof
CN106952732A (en) * 2017-03-02 2017-07-14 湖南云平环保科技有限公司 Laminated film DSSC and preparation method thereof
CN108369990A (en) * 2015-12-21 2018-08-03 Imec 非营利协会 Titanate/ester of doping
CN112142102A (en) * 2020-09-24 2020-12-29 湖北大学 Tantalum-doped titanium dioxide nano film and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104701017A (en) * 2014-12-26 2015-06-10 北京大学深圳研究生院 Titanium dioxide film photo-electrode and preparation method and application thereof
CN104701017B (en) * 2014-12-26 2018-03-13 北京大学深圳研究生院 A kind of titanium deoxid film optoelectronic pole and its preparation method and application
CN108369990A (en) * 2015-12-21 2018-08-03 Imec 非营利协会 Titanate/ester of doping
CN108369990B (en) * 2015-12-21 2022-08-09 Imec 非营利协会 Doped titanates
CN106952732A (en) * 2017-03-02 2017-07-14 湖南云平环保科技有限公司 Laminated film DSSC and preparation method thereof
CN112142102A (en) * 2020-09-24 2020-12-29 湖北大学 Tantalum-doped titanium dioxide nano film and preparation method and application thereof

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