CN102509624A - Preparation of dye-sensitized solar battery from water-solubility and low-reactivity titanium source - Google Patents

Preparation of dye-sensitized solar battery from water-solubility and low-reactivity titanium source Download PDF

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CN102509624A
CN102509624A CN2011103432840A CN201110343284A CN102509624A CN 102509624 A CN102509624 A CN 102509624A CN 2011103432840 A CN2011103432840 A CN 2011103432840A CN 201110343284 A CN201110343284 A CN 201110343284A CN 102509624 A CN102509624 A CN 102509624A
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tio
water
dssc
titanium source
film
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CN102509624B (en
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张青红
郝艳明
王宏志
李耀刚
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Donghua University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to a method for preparing a dye-sensitized solar battery from a water-solubility and low-reactivity titanium source. The method comprises the following steps of: (1) adding a reaction inhibitor or dispergator into a water-solubility titanium source, and then hydrolyzing and refluxing to obtain an anatase-phase TiO2 sol; (2) preparing an anatase-phase TiO2 gel; (3) preparing the TiO2 gel into a sizing material, then depositing the sizing material on a conductive substrate to form a layer of porous TiO2 film, and calcining the porous TiO2 film; and (4) diluting the anatase-phase TiO2 sol obtained in the step (1) , then soaking the calcined porous TiO2 film into the diluted sol, taking the film out, calcining the film to obtain a photo-anode, and finally assembling the obtained photo-anode into the dye-sensitized solar battery. The method disclosed by the invention has a simple technological process, low requirement on equipment, and better environment friendliness; and the dye-sensitized solar battery prepared with the method disclosed by the invention is high in photoelectric conversion efficiency.

Description

Prepare DSSC with titanium source water-soluble, low reaction activity
Technical field
The invention belongs to the preparation field of DSSC, particularly a kind of usefulness is water-soluble, the titanium source of low reaction activity prepares the method for DSSC.
Background technology
1991, professor Gratzel of engineering institutes such as Lausanne, SUI height leader's research group imitated photosynthetic principle, successfully prepared a kind of novel solar cell and be DSSC (DSSCs) (B.O ' Regan; M.Gratzel, Nature, 1991; 353,737-740).Because its abundant raw material, cost is low, preparation technology is simple and photoelectric conversion efficiency is high, thereby caused researcher's extensive concern, surpassed 12% (Q.J.Yu through its photoelectric conversion efficiency of vicennial development; Y.H.Wang, Z.H.Yi, et al.; ACS NANO; 2010,4,6032-6038).
Be different from traditional silicon solar cell, typical DSSC is mainly by conductive substrates, TiO 2Porous membrane, dye molecule, platinum are formed electrode and electrolyte.Its operation principle is that dye molecule excites generation electronics, TiO through absorbing sunlight 2Film then is responsible for collecting dye molecule and is excited the electronics of generation and it is transferred on the conductive substrates dye molecule of the then responsible reduction excitation state of the redox couple in the electrolyte.Core component light anode as DSSC is a research emphasis always, and studying the best light anode material of maximum effects at present is nano-TiO 2Normally used preparation nano-TiO 2Method be hydro thermal method, main titanium source is inorganic salts or titanium the alkoxide for example titanium tetrachloride and the isopropyl titanate of titanium, but these titanium sources are met water and can be produced strong hydrolysis; Produce a large amount of unbodied bulk deposition (C.J.Barbe, F.Arendse, P.Comte; Et al., J.Am.Ceram.Soc., 1997; 80,3157-3171).In addition, the inorganic salts of titanium can discharge a large amount of inorganic ions in hydrolytic process, thereby the electric double layer that these electrodeless ions can compress the nano particle of initial formation causes serious reunion; And the titanium alkoxide can produce various alcohol in hydrolytic process, and these alcohol can optionally be adsorbed on TiO 2On the nanocrystalline crystal face, to TiO 2The pattern of nano particle has complicated influence.In a word, prepare TiO with traditional titanium source 2Process complicated and be difficult to control; Shortcoming such as cause too the growing up of nano particle easily, particle size distribution is inhomogeneous, specific area is low, this all is disadvantageous to manufacturing cost that reduces DSSC and the efficient that improves DSSC.
Usually in order to control hydrolysis of titanium source and TiO 2The pattern of particle, a certain amount of acid, alkali or surfactant can be added into.Obviously this makes TiO 2It is more complicated that the preparation process becomes, and these acid, alkali or surfactant have complicated influence to the performance of DSSC, need be and remove these acid, alkali or surfactant through washing repeatedly, and this has increased cost undoubtedly.
Because TiO 2Contain a large amount of organic substances in the slurry, so in sintering process, can cause TiO owing to organic burning-off 2Can produce a large amount of big space, TiO in the film 2Bridge joint effect between the particle weakens, TiO 2Film can not well contact problems such as conductive substrates.These all can prolong the collection efficiency of the transmission path of electronics, the life-span of reducing electronics, the recombination probability that increases electronics, reduction electronics.
In order to address this problem, use the TiCl of 40mM usually 4The aqueous solution comes burnt TiO 2Film carry out reprocessing (S.Ito, T.N.Murakami, P.Comte, et al., Thin Solid Films, 2008,516,4613-4619).Can improve TiO effectively like this 2The connectedness of film, thus the recombination probability of electronics reduced, prolong the life-span of electronics.But because TiCl 4In hydrolytic process, can discharge a large amount of acidic materials, this can have certain corrosion to conductive substrates, thereby might destroy TiO 2The adhesion of film and conductive substrates, and the collection efficiency of reduction electronics and the photoelectric conversion efficiency of battery (N.Fuke, R.Katoh, A.Islam, et al., Energy Environ.Sci., 2009,2,1205-1209).
Summary of the invention
The technical problem that the present invention will solve provides that a kind of usefulness is water-soluble, the titanium source of low reaction activity prepares the method for DSSC; This procedure is simple, low to the production equipment requirement, and the DSSC that obtains has higher photoelectric conversion efficiency.
A kind of usefulness of the present invention is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, comprising:
(1) water-soluble titanium source with 0.1～0.4M is a presoma, at 90～100 ℃ of following hydrolysis reflow treatment 20～30h, obtains light blue transparent anatase phase TiO behind adding reaction suppressor or the degumming agent 2Colloidal sol, wherein solids content is 8～32g/L;
(2) in the aqueous solution of dihydroxy lactic acid network titanium acid ammonium (TALH, Sigma's aldrich), add reaction suppressor, carry out hydrothermal treatment consists then and obtain anatase phase TiO 2Gel;
The anatase phase TiO that perhaps step (1) is obtained 2Colloidal sol carries out hydrothermal treatment consists and obtains anatase phase TiO 2Gel;
(3) with above-mentioned TiO 2The preparing gel form slurry makes described slurry be deposited on the conductive substrates then, forms the porous TiO that a layer thickness is 5～24 μ m 2Film is again with described porous TiO 2Film is calcined 15～120min, the porous TiO after obtaining calcining down at 400～550 ℃ 2Film;
(4) with the anatase phase TiO of step (1) gained 2The dilution of colloidal sol, the colloidal sol after obtaining diluting is then with the porous TiO after the above-mentioned calcining 2Film is immersed in 5～30min in the colloidal sol after the described dilution, takes out film, calcines 15～120min down at 400～550 ℃, obtains the light anode; The light anode groups that will obtain is at last dressed up DSSC.
Water-soluble titanium source described in the step (1) is dihydroxy lactic acid network titanium acid ammonium TALH; Described reaction suppressor or degumming agent are urea or ammoniacal liquor.
The concentration of the aqueous solution of the dihydroxy lactic acid network titanium acid ammonium TALH described in the step (2) is 0.1～2M.
The described reaction suppressor of step (2) is one or more the mixing in urea, ammoniacal liquor or the nitric acid; Described hydrothermal treatment consists temperature is 150～240 ℃.
TiO in the slurry described in the step (3) 2The mass content of nano particle is 17%～30%, and the preparation method of said slurry is with TiO 2Gel is used deionized water and washing with alcohol successively, and the deposition that then washing is obtained is distributed in the decentralized medium, adds binding agent again, and stirring, ultrasonic is revolved steaming at last and promptly got.
Above-mentioned decentralized medium is terpinol or deionized water, and binding agent is ethyl cellulose (M70) or polyethylene glycol (PEG20000).
Described being deposited as through silk screen printing, blade coating or spraying process of step (3) makes slurry be deposited on conductive substrates.
Conductive substrates described in the step (3) is the SnO of doped with fluorine 2Electro-conductive glass (SnO 2: F, be called for short FTO) or indium tin oxide-coated glass (being called for short the ITO electro-conductive glass).
The assemble method of the DSSC described in the step (4) is for to separate to electrode resulting smooth anode and platinum with the sarin film, filling electrolyte after the encapsulation promptly is assembled into DSSC.
Anatase phase TiO in the colloidal sol after the dilution described in the step (4) 2Solids content is 3～16g/L in the colloidal sol.
Osmotic treated process purpose is to improve TiO in the step (4) 2The connectedness of porous membrane, and strengthen porous TiO 2Adhesion between film and the conductive substrates.
The present invention prepares the high efficiency dye sensitization solar battery with titanium source TALH water-soluble, low reaction activity has two parts to constitute: at first; TALH is a kind of titanium source of water-soluble low reaction activity; Simple because of its hydrolytic process, controllability is strong, prepared have rational particle diameter, narrower particle size distribution, good dispersion, than the anatase phase TiO of bigger serface 2Nanocrystalline, and with this nanocrystalline TiO for preparing porous 2Film; Secondly, the anatase phase TiO for preparing with water-soluble titanium source 2Colloidal sol does not contain any difficult volatilization impurity near neutral, is used for TiO 2Porous membrane carries out the connectedness that reprocessing can improve film effectively, improves TiO 2Adhesion between film and the conductive substrates, thus the life-span of electronics, the recombination probability of minimizing electronics, the collection efficiency of raising electronics improved.Finally, through density of photocurrent (I)-characteristic test shows of photovoltage (V), the DSSC for preparing with water-soluble titanium source TALH can produce the photoelectric conversion efficiency above 9%, has good commercial application prospect.
The present invention is a presoma with titanium source TALH water-soluble, low reaction activity, the anatase phase TiO for preparing through simple hydrothermal treatment consists process 2Nanocrystalline have particle diameter rationally, narrower, the good dispersion of particle size distribution and the big advantage of specific area, with this TiO 2The nanocrystalline light anode that is used to prepare DSSC can be obtained good effect, and this method technical process is simple, low for equipment requirements, friendly more to environment.
The present invention is the anatase phase TiO of presoma preparation with titanium source TALH water-soluble, low reaction activity 2Colloidal sol does not contain any difficult volatilization impurity near neutral, can be used for porous TiO 2Film carries out the reprocessing modification.With traditional T iCl 4Reprocessing is compared, and uses anatase phase TiO 2Can improve the connectedness of film after colloidal sol is handled porous membrane more effectively, improve TiO 2Adhesion between film and the conductive substrates, thus the collection efficiency of the life-span of electronics, the recombination probability that reduces electronics, raising electronics, the short circuit current and the photoelectric conversion efficiency of raising battery improved.
Beneficial effect:
(1) technical process of the present invention is simple, low for equipment requirements, friendly more to environment;
(2) the present invention uses water-soluble titanium source TALH to prepare nano-TiO 2Technology simple controllable property strong, friendly more to environment, and the TiO of preparation 2Nanocrystalline quality is high; Prepared anatase phase TiO 2Colloidal sol is near neutral, and degree of crystallinity height, good dispersion, stability by force, the particle size homogeneous;
(3) well-formed's that obtains of the present invention light anode has obtained higher photoelectric conversion efficiency after it is assembled into DSSC.
Description of drawings
Fig. 1 is embodiment 1 anatase phase TiO 2Nanocrystalline and anatase be TiO mutually 2The X-ray diffractogram of colloidal sol;
Fig. 2 is the TiO of embodiment 1 Hydrothermal Preparation 2Nanocrystalline transmission electron microscope photo;
Fig. 3 is the TiO of embodiment 2 Hydrothermal Preparation 2Nanocrystalline N 2The adsorption-desorption isothermal curve;
Fig. 4 be embodiment 4 preparation without the TiO that handles later 2The field emission scanning electron microscope photo of the surface topography of film;
Fig. 5 is the TiCl that uses of embodiment 4 preparations 4The TiO of aqueous solution reprocessing 2The field emission scanning electron microscope photo of the surface topography of film;
Fig. 6 be embodiment 4 preparation with anatase phase TiO 2The TiO of colloidal sol osmotic treated 2The field emission scanning electron microscope photo of the surface topography of film;
Fig. 7 is the I-V of three kinds of DSSCs of embodiment 4 preparations.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) TALH with the 2M of 49ml joins in the 450ml deionized water, stirs 2min, 3g urea is added wherein again, stirs 5min, and this mixed solution is transferred in the there-necked flask, behind 90 ℃ of refluxed hydrolysis 20h, can obtain blue transparent TiO 2Colloidal sol; Getting the vacuumize of 50ml colloidal sol obtains powder and carries out X-ray diffraction (XRD) and analyze;
(2) get 300ml colloidal sol and join in the water heating kettle, obtain white titania gel behind 200 ℃ of hydrothermal treatment consists 24h;
(3) above-mentioned titania gel is used deionized water and washing with alcohol once successively, the white precipitate after the washing is distributed in the 200ml absolute ethyl alcohol, wherein TiO 2Content be about 4.8g; Getting 75ml is dried to powder and carries out the analysis of XRD and transmission electron microscope (TEM); 1.5g ethyl cellulose M70 is dissolved in the 30ml absolute ethyl alcohol, joins 125mlTiO afterwards 2In the suspension, and stir and each 10min of ultrasonic dispersion, subsequently the adding of 10g terpinol wherein and is once more stirred and each 10min of ultrasonic dispersion, rotation is at last steamed to certain viscosity, processes TiO 2Slurry; The method of use silk screen printing prepares thickness on the FTO electro-conductive glass be the porous TiO of 24 μ m 2Film is calcined 30min with this film at 500 ℃;
(4) film after will calcining at room temperature is immersed in one times of colloidal sol of dilution, keeps 10min.Film after the infiltration at 500 ℃ of calcining 30min, is taken out after temperature drops to 80 ℃ and is immersed in the dye solution, and maintenance 24h is assembled into DSSC after the taking-up.
Fig. 1 is the TiO for preparing through hydrolysis process in the present embodiment 2The TiO of colloidal sol (a) and hydrothermal treatment consists preparation 2The X-ray diffraction of nanocrystalline (b) (XRD) figure, from figure, can see colloidal sol prepared in the present embodiment and nanocrystalline in TiO 2Be the anatase phase, and the XRD diffraction maximum of colloidal sol there be tangible wideization, comprise superfine Ti O in this proof colloidal sol 2Nano particle.
The TiO of Fig. 2 for preparing in the present embodiment 2Nanocrystalline transmission electron microscope (TEM) image, as can be seen from the figure TiO 2Crystallite dimension is 10nm, and particle size distribution is even.
Embodiment 2
(1) the 2M TALH with 196ml joins in the 304ml deionized water, stirs 5min, 30ml ammoniacal liquor is added dropwise to wherein again, stirs 5min, and this mixed solution is transferred in the there-necked flask, behind 100 ℃ of refluxed hydrolysis 30h, can obtain blue transparent TiO 2Colloidal sol;
(2) TALH with the 2M of 49ml joins in the 450ml deionized water, stirs 5min, 3g urea is added wherein again, stirs 5min, and this mixed solution is joined in the water heating kettle, obtains the titania gel of white behind 200 ℃ of hydrothermal treatment consists 24h;
(3) above-mentioned titania gel is used deionization and washing with alcohol once successively, the white precipitate after the washing is distributed in the 200ml absolute ethyl alcohol, wherein TiO 2Content be about 8g, get 100ml and be dried to powder and carry out N 2The adsorption-desorption isothermal curve is analyzed.The 2g ethyl cellulose is dissolved in the 30ml absolute ethyl alcohol, joins 100mlTiO afterwards 2In the suspension, and stir and each 10min of ultrasonic dispersion, subsequently the adding of 13.2g terpinol wherein and is once more stirred and each 10min of ultrasonic dispersion, rotation is at last steamed to certain viscosity, processes TiO 2Slurry; Using knife coating on the FTO electro-conductive glass, to prepare thickness is the porous TiO of 5 μ m 2Film is calcined 30min with this film at 500 ℃;
(4) film after will calcining at room temperature is immersed in one times of colloidal sol of dilution, keeps 10min; Film after the infiltration at 500 ℃ of calcining 30min, is taken out after temperature drops to 80 ℃ and is immersed in the dye solution, and maintenance 24h is assembled into DSSC after the taking-up.
Shown in Figure 3 is the prepared TiO of present embodiment 2Nanocrystalline N 2The adsorption-desorption isothermal curve, analysis can obtain TiO 2Specific area be 108m 2/ g.
Embodiment 3
(1) TALH with the 2M of 49ml joins in the 450ml deionized water, stirs 2min, 3g urea is added wherein again, stirs 5min, and this mixed solution is transferred in the there-necked flask, behind 95 ℃ of refluxed hydrolysis 24h, can obtain blue transparent TiO 2Colloidal sol;
(2) the 14ml red fuming nitric acid (RFNA) is added dropwise among the TALH of 2M of 50ml, stirs 5min, this mixed solution is joined in the water heating kettle, obtain the titanium dioxide precipitation of brown behind 240 ℃ of hydrothermal treatment consists 24h;
(3) above-mentioned titanium dioxide precipitation is used deionization and washing with alcohol once successively, the deposition of the brown after the washing is distributed in the 200ml absolute ethyl alcohol, wherein TiO 2Content be about 8g.The 2g ethyl cellulose is dissolved in the 30ml absolute ethyl alcohol, joins 100ml TiO afterwards 2In the suspension, and stir and each 10min of ultrasonic dispersion, subsequently the adding of 13.2g terpinol wherein and is once more stirred and each 10min of ultrasonic dispersion, rotation is at last steamed to certain viscosity, processes TiO 2Slurry; Using knife coating on the FTO electro-conductive glass, to prepare thickness is the porous TiO of 18 μ m 2Film is calcined 30min with this film at 500 ℃;
(4) film after will calcining at room temperature is immersed in one times of colloidal sol of dilution, keeps 10min; Film after the infiltration at 450 ℃ of calcining 30min, is taken out after temperature drops to 80 ℃ and is immersed in the dye solution, and maintenance 24h is assembled into DSSC after the taking-up.
Embodiment 4
(1) TALH with the 2M of 49ml joins in the 450ml deionized water, stirs 5min, 3g urea is added wherein again, stirs 5min, and this mixed solution is transferred in the there-necked flask, behind 95 ℃ of refluxed hydrolysis 24h, can obtain blue transparent TiO 2Colloidal sol;
(2) TALH with the 2M of 49ml joins in the 450ml deionized water, stirs 5min, 3g urea is added wherein again, stirs 5min, and this mixed solution is joined in the water heating kettle, obtains the titania gel of white behind 200 ℃ of hydrothermal treatment consists 24h;
(3) above-mentioned titania gel is used deionization and washing with alcohol once successively, the white precipitate after the washing is distributed in the 200ml absolute ethyl alcohol, wherein TiO 2Content be about 8g; The 2g ethyl cellulose is dissolved in the 30ml absolute ethyl alcohol, joins 100ml TiO afterwards 2In the suspension, and stir and each 10min of ultrasonic dispersion, subsequently the adding of 13.2g terpinol wherein and is once more stirred and each 10min of ultrasonic dispersion, rotation is at last steamed to certain viscosity, processes TiO 2Slurry; The method of use silk screen printing prepares thickness on the FTO electro-conductive glass be the porous TiO of 15 μ m 2Film is calcined 30min with this film at 500 ℃;
(4) film after the part calcining at room temperature is immersed in one times of colloidal sol of dilution, keeps 10min, another part is used TiCl 4The aqueous solution handle.Two kinds of films of handling are calcined 30min at 500 ℃.After temperature drops to 80 ℃, take out and be immersed in the dye solution, keep 24h, be assembled into DSSC after the taking-up.
Shown in Figure 4 for present embodiment preparation not with the anatase TiO that glue penetration handles that mixes 2The surface topography of porous membrane can be found out TiO on scheming 2Contact between the particle is loose, and has big space and pin hole to exist;
The TiCl that uses for the present embodiment preparation shown in Figure 5 4The TiO that the aqueous solution is handled 2The surface topography of porous membrane can be found out TiO on scheming 2Connectedness between the particle has obtained good improvement, and particle size also has increase;
Shown in Figure 6 for present embodiment preparation with anatase phase TiO 2The TiO of colloidal sol osmotic treated 2The surface topography of porous membrane can be found out on scheming, with TiCl 4The film of handling is compared, and uses TiO 2The colloidal sol osmotic treated can be improved TiO better 2Connectedness between the particle, same particle size also has increase;
Fig. 7 can find out with anatase phase TiO for the I-V curve chart of the various DSSCs of present embodiment preparation 2The density of photocurrent and the energy conversion efficiency of the DSSC of colloidal sol osmotic treated are the highest, use TiCl 4The density of photocurrent of the DSSC that the aqueous solution is handled and energy conversion efficiency next, the density of photocurrent and the energy conversion efficiency of DSSC of not passing through any reprocessing is minimum.

Claims (10)

1. one kind prepares the method for DSSC with titanium source water-soluble, low reaction activity, comprising:
(1) in the water-soluble titanium source of 0.1～0.4M, adds reaction suppressor or degumming agent, at 90～100 ℃ of following hydrolysis reflow treatment 20～30h, obtain anatase phase TiO then 2Colloidal sol, wherein solids content is 8～32g/L;
(2) in the aqueous solution of dihydroxy lactic acid network titanium acid ammonium TALH, add reaction suppressor, carry out hydrothermal treatment consists then and obtain anatase phase TiO 2Gel;
The anatase phase TiO that perhaps step (1) is obtained 2Colloidal sol carries out hydrothermal treatment consists and obtains anatase phase TiO 2Gel;
(3) with above-mentioned TiO 2The preparing gel form slurry makes described slurry be deposited on the conductive substrates then, forms the porous TiO that a layer thickness is 5～24 μ m 2Film is again with described porous TiO 2Film is calcined 15～120min, the porous TiO after obtaining calcining down at 400～550 ℃ 2Film;
(4) with the anatase phase TiO of step (1) gained 2The dilution of colloidal sol, the colloidal sol after obtaining diluting is then with the porous TiO after the above-mentioned calcining 2Film is immersed in 5～30min in the colloidal sol after the described dilution, takes out film, calcines 15～120min down at 400～550 ℃, obtains the light anode; The light anode groups that will obtain is at last dressed up DSSC.
2. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: the water-soluble titanium source described in the step (1) is dihydroxy lactic acid network titanium acid ammonium TALH; Described reaction suppressor or degumming agent are urea or ammoniacal liquor.
3. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: the concentration of the aqueous solution of the dihydroxy lactic acid network titanium acid ammonium TALH described in the step (2) is 0.1～2M.
4. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: the described reaction suppressor of step (2) is one or more the mixing in urea, ammoniacal liquor or the nitric acid; Described hydrothermal treatment consists temperature is 150～240 ℃.
5. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: TiO in the slurry described in the step (3) 2The mass content of nano particle is 17%～30%, and the preparation method of said slurry is with TiO 2Gel is used deionized water and washing with alcohol successively, and the deposition that then washing is obtained is distributed in the decentralized medium, adds binding agent again, and stirring, ultrasonic is revolved steaming at last and promptly got.
6. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, and it is characterized in that: above-mentioned decentralized medium is terpinol or deionized water, and binding agent is ethyl cellulose or polyethylene glycol.
7. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: described being deposited as through silk screen printing, blade coating or spraying process of step (3) makes slurry be deposited on conductive substrates.
8. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, and it is characterized in that: the conductive substrates described in the step (3) is the SnO of doped with fluorine 2Electro-conductive glass or indium tin oxide-coated glass.
9. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC; It is characterized in that: the assemble method of the DSSC described in the step (4) is for to separate to electrode resulting smooth anode and platinum with the sarin film; Filling electrolyte after the encapsulation promptly is assembled into DSSC.
10. a kind of usefulness according to claim 1 is water-soluble, the titanium source of low reaction activity prepares the method for DSSC, it is characterized in that: anatase phase TiO in the colloidal sol after the dilution described in the step (4) 2Solids content is 3～16g/L in the colloidal sol.
CN201110343284.0A 2011-11-03 2011-11-03 Preparation of dye-sensitized solar battery from water-solubility and low-reactivity titanium source Expired - Fee Related CN102509624B (en)

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CN102903536A (en) * 2012-09-29 2013-01-30 彩虹集团公司 Preparation method of titanium dioxide film for nanocrystalline solar cell
CN103021568A (en) * 2012-12-10 2013-04-03 彩虹集团公司 Preparation method of dye-sensitized solar cell slurry
CN103903859A (en) * 2012-12-27 2014-07-02 中国科学院上海硅酸盐研究所 Method for preparing photoanode of dye-sensitized solar cell through coating
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