CN102306550A - Method for preparing nano-branched titanium dioxide photoanode of dye sensitized solar cell - Google Patents
Method for preparing nano-branched titanium dioxide photoanode of dye sensitized solar cell Download PDFInfo
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- 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
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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
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a method for preparing a nano-branched titanium dioxide photoanode of a dye sensitized solar cell and relates to a photoanode of a solar cell. The method comprises the following steps of: cleaning conductive glass; depositing a ZnO nanorod array template on the surface of the conductive glass and dipping in a mixed solution of (NH4)2TiF6 and boric acid to obtain titanium dioxide nanorods; dipping the calcined titanium dioxide nanorods in a TiCl4 solution, putting into a reaction kettle, leaning the conductive glass against the inner wall of the reaction kettle, adding a mixed solution of HCl and tetrabutyl titanate and performing hydrothermal reaction to obtain the nano-branched titanium dioxide photoanode of the dye sensitized solar cell; mixing tetrabutyl titanate and HF, performing hydrothermal reaction, taking out white powder, washing, performing centrifugal separation, drying, putting the product into an absolute ethanol solution to obtain the suspension of titanium dioxide nano-slices; and coating a film layer of titanium dioxide nano-slice granules on the surface of the obtained product to obtain the final product.
Description
Technical field
The present invention relates to a kind of solar battery light anode, especially relate to a kind of preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode.
Background technology
1991, Switzerland
And partner
[1]Utilize rhodium complex as sensitizer first, develop a kind of new dye sensitization solar battery.This battery as the light anode, utilizes it to the absorption of dyestuff with photoelectricity is carried out in the conduction of excitation electron transform with the titania nanoparticles of porous.Up to the present, the efficient of this battery surpasses 11%
[2]Yet, although the titania nanoparticles of porous has high specific area,, the randomness of grain structure makes the electron transport inefficiency, and granular boundary makes the compound of light induced electron-hole easily, so that battery efficiency is difficult to get a promotion.In order to address this problem, in recent years, people begin to explore one dimension (1-D) TiO of preparation high-sequential in different substrates
2Nano-array
[3-6]Research shows that the array of this high-sequential has the TiO of ratio
2The electron transport efficient that nano particle is higher.At present, the method for preparing this 1-D nanostructure mainly comprises ZnO template, Al
2O
3Template, anode oxidation method and hydro thermal method etc.The TiO of anode oxidation method preparation wherein
2Nanotube is the most orderly, yet anode oxidation method often can only be at Titanium substrate surface preparation TiO
2, the design that so just causes battery must be a back side illuminaton, and the light anode of anode oxidation method preparation is because the existence on barrier layer, fill factor, curve factor is comparatively low, thereby causes efficient to be difficult to get a promotion.Hydro thermal method and template are simple to operate, are fit to large-scale production, have begun in recent years to be widely used.Hydro thermal method can be directly at the fine and close TiO of conductive glass surface growth
2Nano-wire array, but have adhesion difference shortcoming, and the TiO for preparing
2Nano wire is not the most excellent anatase crystals (anatase) of photoelectric properties for being mostly rutile-type (rutile).Template can prepare tens microns long nano wires, yet because through twice deposition, the diameter of nano-array is often bigger, thereby having reduced the surface area that dyestuff adsorbs, efficient is difficult to be improved.
List of references:
[1]B.O’Regan?and?M.Gratzel，Nature(London)，353，7371991。
[2]M.
J.Photochem.Photobiol.A?Chem.164(2004)。
[3]Xinjian?Feng，Craig?A.Grimes
*et?al.，Nano?Lett.，Vol.8，No.11，200。
[4]Bin?Liu?and?Eray?S.Aydil
*，J.AM.CHEM.SOC.2009，131，3985-3990-3985。
[5]T.Rattanavoravipa?et?al.，Solar?Energy?Materials&Solar?Cells?92(2008)1445-144。
[6]Gopal?K.Mor，Karthik?Shankar，Maggie?Paulose，Oomman?K.Varghese，and?Craig?A.Grimes
*，Nano?Lett.，Vol.6，No.2，2006。
[7]Deki，S.；Iizuka，S.；Horie，A.；Mizuhata，M.；Kajinami，A.Chem.Mater.2004，16，1747。
[8]Lee，J.-H.；Leu，I.-C.；Hsu，M.-C.；Chung，Y.-W.；Hon，M.-H.J.Phys.Chem.B?2005，109，13056。
Summary of the invention
The object of the invention is intended to the problem to above-mentioned prior art existence, and a kind of utilance that can significantly increase light is provided, and promotes the preparation method of the dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode of cell photoelectric conversion performance.
The present invention includes following steps:
1) with after the electro-conductive glass cleaning, dry up for use;
In step 1), said electro-conductive glass can adopt FTO electro-conductive glass etc., and the size of said electro-conductive glass can be 1cm * 2cm; Said cleaning can be put into acetone, deionized water, absolute ethyl alcohol ultrasonic cleaning successively with electro-conductive glass, and the time of ultrasonic cleaning can be 20～45min.
2) utilize galvanostatic method in conductive glass surface deposition layer of ZnO nanometer stick array template;
In step 2) in, the said galvanostatic method of utilizing can adopt two electrode systems in FTO surface deposition layer of ZnO nanometer stick array template, and said two electrode systems are: electro-conductive glass is a work electrode, and the conduct of Pt electrode is to electrode.Electrolyte is by 1～10mMZn (NO
3)
2With 1～10mM C
6H
12N
4Form, at the condition deposit 30～60min of constant-temperature constant-current, through for use after the washed with de-ionized water.
3) with step 2) electro-conductive glass of preparation places and contains (NH
4)
2TiF
6Behind dipping in the boric acid mixed solution, take out, clean, obtain titanium dioxide nano-rod, dry the back calcining;
In step 3), said (NH
4)
2TiF
6Concentration can be 0.05～0.1M, the concentration of said boric acid can be 0.15～0.5M; The time of said dipping can be 3～5h; Said cleaning can be adopted washed with de-ionized water; The temperature of said calcining can be 450 ℃, and the time of calcining can be 2h, and the heating rate of calcining can be 5 ℃/min.
4) titanium dioxide nano-rod after will calcining is immersed in TiCl
4In the solution, place agitated reactor then, electro-conductive glass is leaned to the inwall in agitated reactor, in agitated reactor, add the mixed solution that contains HCl and butyl titanate, carry out hydro-thermal reaction, get dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode.
In step 4), said TiCl
4The concentration of solution can be 0.1～0.7M, and the time of said immersion can be 30～60min; The quality percentage mark of said HCl solution can be 10%～27%; The quality percentage mark of said butyl titanate can be 1%～6%; The temperature of said hydro-thermal reaction can be 150～180 ℃, and the time of hydro-thermal reaction can be 1.5～20h.
5) titanium dioxide nanoplate is synthetic: butyl titanate and HF are mixed, place agitated reactor, and airtight; After the hydro-thermal reaction, the gained white powder is taken out the centrifugation of washing back; The oven dry, products therefrom is placed ethanol solution, obtain the suspension of titanium dioxide nanoplate after; Rete at the product surface-coated layer of titanium dioxide nanometer sheet particle of step 4) gained promptly gets dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode.
In step 5), the concentration of said HF can be 23%～46%; The temperature of said hydro-thermal reaction can be 150～180 ℃, and the time of hydro-thermal reaction can be 12～24h; Said washing can be successively with deionized water, sodium hydroxide solution, absolute ethanol washing, and the concentration of said sodium hydroxide solution can be 0.1～1M.The rete of said product surface-coated layer of titanium dioxide nanometer sheet particle at the step 4) gained, knife coating capable of using is at the rete of the product surface-coated layer of titanium dioxide nanometer sheet particle of step 4) gained.
The present invention combines the advantage of template and hydro thermal method, utilizes the method for electro-deposition to prepare orderly One-Dimensional ZnO nanometer rods template at the FTO conductive glass surface, and utilizes the orderly TiO of template growth one deck
2Nanometer stick array.Utilize the method for hydro-thermal to grow the TiO of the minor matters shape that mixes crystal formation at last
2Nanometer stick array applies the regular cuboid sheet TiO of one deck in nanorod surfaces simultaneously
2Particle shows through research: the minor matters shape TiO of generation
2Nanometer rods helps increasing the adsorption area of dyestuff; Be in the cuboid TiO on nanometer rods top
2Nano-sheet has not only remedied the defective that electrode exists, and has also increased surface area simultaneously; The nanometer sheet that covers the nanometer rods top then plays the internal reflection effect to incident light, plays an important role for the raising of efficiency of light absorption.This method has not only that method is simple, controllability is strong, be easy to advantage such as industrialization, and formed TiO after the hydrothermal treatment consists
2Nanometer sheet is the mixed crystal of anatase and rutile, and high-temperature calcination is handled once more, has avoided nanometer rods bottom when high-temperature calcination to be prone to the phenomenon of cracking.
Description of drawings
Fig. 1 is about the SEM figure of the ZnO nanometer stick array of 1.5 μ m for length.In Fig. 1, scale is 2 μ m.
Fig. 2 is about the EDS spectrogram of the ZnO nanometer stick array of 1.5 μ m for length.In Fig. 2, abscissa is energy E nergy, and KeV, ordinate are intensity Counts.
Fig. 3 utilizes the TiO of ZnO nanometer stick array for the template preparation
2The SEM figure of nanometer stick array.In Fig. 3, scale is 2 μ m; Length is about 1.4 μ m, and diameter is about 170～200nm.
Fig. 4 utilizes the TiO of ZnO nanometer stick array for the template preparation
2The EDS spectrogram of nanometer stick array.In Fig. 4, abscissa is energy E nergy, and KeV, ordinate are intensity Counts; Show that ZnO has been converted into TiO
2
Fig. 5 is single TiO
2The FE-TEM figure on nanometer rods top.In Fig. 5, scale is 100nm, can be clear that by Fig. 5, and nanometer rods is the hollow structure of top closure.
Fig. 6 is the TiO of preparation
2The SEM shape appearance figure of nanometer rods after carrying out the different water thermal response time under 180 ℃ of conditions.In Fig. 6, figure a scale is 2 μ m, and the scale of enlarged drawing is 200nm; Figure b scale is 1 μ m, and the scale of enlarged drawing is 200; Figure c scale is 1 μ m, and the scale of enlarged drawing is 200nm; Figure d scale is 5 μ m, and the scale of enlarged drawing is 500nm; Figure a is reaction 1.5h, and figure b is 2h, and figure c is 2.5h, and figure d is 3h, and wherein, b and c can find out tangible minor matters shape pattern.
Fig. 7 is the XRD spectra of 3 different samples.In Fig. 7, curve a is the XRD spectra of ZnO nanometer stick array; Curve b is TiO
2The XRD spectra of nanometer stick array; Curve c is TiO
2The XRD spectra of nanometer stick array, abscissa are 2Theta (angle), and ordinate is diffraction relative intensity Intensity (a.u.), and A represents TiO
2Anatase phase (Anatase), R represents TiO
2Rutile phase (Rutile); Except being labeled as the diffraction maximum of A and R, other are substrate of glass (SnO
2) and the diffraction maximum of ZnO.
Fig. 8 is the SEM surface topography map that is coated in the titanium dioxide nanoplate on nanometer minor matters surface.In Fig. 8, scale is 500nm.
Fig. 9 is the I～V curve chart with the DSSC of the anode groups dress of not sharing the same light.In Fig. 9, abscissa is voltage (V), and abscissa is current density (mA/cm
2); Curve a is untreated TiO
2Nanometer rods, curve b is the TiO of minor matters shape mixing crystal formation
2Nanometer rods, curve c is the minor matters shape TiO that sheet-like particle is modified
2Nanometer rods.
Embodiment
Following examples will combine accompanying drawing that the present invention is further described.
The flow process of preparation dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode is: at first, and through the method for electro-deposition, at conductive glass surface deposition layer of ZnO nanometer stick array.Then, the method through liquid deposition is converted into TiO with the ZnO nanometer stick array
2Nanometer stick array.With TiO
2Nanometer stick array is a Seed Layer, in hydrothermal condition, and growth minor matters shape TiO
2Nanometer rods.At last, with synthetic TiO
2Nanometer sheet applies and minor matters shape TiO
2Nanorod surfaces forms scattering layer.
Embodiment 1
1) FTO electro-conductive glass (1cmx2cm) is put into acetone respectively, deionized water, ultrasonic cleaning 30min in the absolute ethyl alcohol then, dries up for use.
2) utilize galvanostatic method on FTO, to deposit layer of ZnO nanometer stick array template.It is work electrode that two electrode systems: FTO is adopted in electro-deposition, and the conduct of Pt electrode is to electrode.Electrolyte is by 5mM Zn (NO
3)
2With 5mM C
6H
12N
4Form.At the condition deposit 60min of constant-temperature constant-current, through for use after the washed with de-ionized water.As illustrated in fig. 1 and 2; Electro-deposition through 60min is about 1.5 μ m ± 25nm, and the ZnO nanometer stick array of the about 150 ± 20nm of diameter is grown on the FTO; From Fig. 1 and 2, can find out; The ZnO nanometer rods is the hexagon of rule, because the out-of-flatness on FTO surface, the nanometer rods of preparing not is very in order vertical.
3) with step 2) the ZnO nanometer rods template of preparation places and contains 0.05M (NH
4)
2TiF
6In 0.15M boric acid mixed solution.Room temperature dipping 3～5h.Take out, use washed with de-ionized water.Obtain titanium dioxide nano-rod.Put into Muffle furnace after it is dried, at 450 ℃ temperature lower calcination 2h, heating rate is 5 ℃/min.The TiO of this step gained
2The pattern of nanometer rods can be found out from Fig. 3 shown in Fig. 3 and 4, relative ZnO nanometer rods template, TiO
2Nanometer rods is consistent on whole pattern, and its course of reaction can be represented by following equation
[7,8]:
TiF
6 2-+2H
2O＝TiO
2+6F
-+4H
+ (1)
H
3BO
3+4HF＝HBF
4+3H
2O (2)
ZnO+2H
+＝Zn
2++H
2O (3)
TiO
2The formation of nanometer rods is divided into etching and the TiO of ZnO
2Two parts of deposition.Can obviously find out in the TEM spectrogram from Fig. 5: the TiO of formation
2Nanometer rods is the structure of hollow, and the diameter of the diameter of its inner chamber and ZnO nanometer rods is consistent.Analysis through XRD and EDS can be known: after the immersion through 3～5h, the ZnO major part is dissolved, and in the EDS spectrogram, can find out, has only the existence of a small amount of ZnO in the nanometer rods.Through 450 ℃ of calcinings, TiO
2Change anatase crystal into by amorphous state.
4) with burnt TiO
2Nanometer rods is immersed in 0.1～0.7M TiCl
430～60min in the solution places the 100ml agitated reactor then, and the FTO electro-conductive glass leans to the inwall in agitated reactor.Then, in agitated reactor, add 50ml HCl (mass fraction is 10%～27%) solution, the adding volume fraction is 1%～6% butyl titanate in solution, stirs. at last, agitated reactor is carried out the hydro-thermal reaction of 1.5h under 150～180 ℃.Shown in Fig. 6 a, through after the hydro-thermal reaction of 1.5h, at original T iO
2The intensive nano wire of having grown between the slit of nanometer rods, nanowire length and diameter are about 100nm and 15nm.Nano wire the surface can see " bud shape " nanometer minor matters.
5) a certain amount of butyl titanate and HF are mixed, place agitated reactor, airtight.Agitated reactor is put into 150～180 ℃ of baking ovens, hydro-thermal reaction 12～24h.After the reaction, the gained white powder is taken out, use deionized water successively, sodium hydroxide solution, absolute ethanol washing, centrifugation then, oven dry.Products therefrom is placed a certain amount of ethanol solution, and stirred for several hour obtains the suspension of titanium dioxide nanoplate.Then, utilize the rete of knife coating at minor matters shape nano wire (step 4) products therefrom) surface-coated layer of titanium dioxide nanometer sheet particle.
Embodiment 2
Three steps (step 1), 2) of front, 3)) identical with embodiment 1.
4) burnt titanium dioxide nano-rod is immersed in 0.1～0.5M TiCl
430-60min in the solution places the 100ml agitated reactor then, and the FTO electro-conductive glass leans to the inwall in agitated reactor.Then, in agitated reactor, add 50ml HCl (mass fraction is 10%～27%) solution, the adding volume fraction is 1%～6% butyl titanate in solution, stirs.At last, agitated reactor is carried out the hydro-thermal reaction of 2h under 150～180 ℃.After the 2h hydro-thermal, the surface topography of light anode is shown in Fig. 6 b: TiO
2The superficial growth of nanometer rods the nano wire of minor matters shapes, the sign through XRD (referring to Fig. 7 c) can prove, the nano wire of these minor matters shapes is the TiO of rutile phase
2
5) a certain amount of butyl titanate and HF are mixed, place agitated reactor, airtight.Agitated reactor is put into 150～180 ℃ of baking ovens, hydro-thermal reaction 12～24h.After the reaction, the gained white powder is taken out, use deionized water successively, sodium hydroxide solution, absolute ethanol washing, centrifugation then, oven dry.Products therefrom is placed a certain amount of ethanol solution, and stirred for several hour obtains the suspension of titanium dioxide nanoplate.Then, utilize the rete of knife coating at minor matters shape nano wire (step 4) products therefrom) surface-coated layer of titanium dioxide nanometer sheet particle.
Embodiment 3
Three steps (step 1), 2) of front, 3)) identical with embodiment 1.
4) burnt titanium dioxide nano-rod is immersed in 0.1～0.7M TiCl
430-60min in the solution places the 100ml agitated reactor then, and the FTO electro-conductive glass leans to the inwall in agitated reactor.Then, in agitated reactor, add 50ml HCl (mass fraction is 10%～27%) solution, the adding volume fraction is 1%～6% butyl titanate in solution, stirs.At last, agitated reactor is carried out the hydro-thermal reaction of 2.5h under 150～180 ℃.After the 2.5h hydro-thermal, the surface topography of light anode is shown in Fig. 6 c: most of TiO
2Nanometer rods is covered by minor matters shape nano wire, and whole pattern presents the one-dimensional array structure of top bunch shape.
5) a certain amount of butyl titanate and HF are mixed, place agitated reactor, airtight.Agitated reactor is put into 150～180 ℃ of baking ovens, hydro-thermal reaction 12～24h.After the reaction, the gained white powder is taken out, use deionized water successively, sodium hydroxide solution, absolute ethanol washing, centrifugation then, oven dry.Products therefrom is placed a certain amount of ethanol solution, and stirred for several hour obtains the suspension of titanium dioxide nanoplate.Then, utilize the rete of knife coating at minor matters shape nano wire (step 4) products therefrom) surface-coated layer of titanium dioxide nanometer sheet particle.
Embodiment 4
Three steps (step 1), 2) of front, 3)) identical with embodiment 1.
4) burnt titanium dioxide nano-rod is immersed in 0.1～0.7M TiCl
430～60min in the solution places the 100ml agitated reactor then, and the FTO electro-conductive glass leans to the inwall in agitated reactor.Then, (mass fraction is 10%～27% solution, and the adding volume fraction is 1%～6% butyl titanate in solution, stirs in agitated reactor, to add 50ml HCl.At last, with agitated reactor at 150～180 ℃ of following hydro-thermal reaction 3h.Through after the hydro-thermal reaction of 3h, the gold redrock nano line is fully with TiO
2Nanometer stick array covers.The nano wire that can be clearly seen that bunch shape from Fig. 6 d covers the surface, and single nano-wire presents hexahedron structure, and the top presents square.
5) a certain amount of butyl titanate and HF are mixed, place agitated reactor, airtight.Agitated reactor is put into 150～180 ℃ of baking ovens, hydro-thermal reaction 12～24h.After the reaction, the gained white powder is taken out, use deionized water successively, sodium hydroxide solution, absolute ethanol washing, centrifugation then, oven dry.Products therefrom is placed a certain amount of ethanol solution, and stirred for several hour obtains the suspension of titanium dioxide nanoplate.Then, utilize the rete of knife coating at minor matters shape nano wire (step 4) products therefrom) surface-coated layer of titanium dioxide nanometer sheet particle.
Specific embodiment and income effect are by shown in Fig. 6, Fig. 8 and the table 1:
Table 1TiO
2Minor matters shape nano-TiO on the nanometer stick array
2Growth
The present invention utilizes the method for electro-deposition to deposit the layer of ZnO nanometer stick array at the FTO conductive glass surface, then, is template with the ZnO nanometer stick array, utilizes the method for liquid phase etching and deposition on template, to generate the orderly TiO of one deck
2Nanometer stick array.Then, utilize hydro thermal method to prepare the minor matters shape TiO that mixes crystal formation (anatase/rutile) in substrate of glass first
2Nanometer stick array simultaneously, through changing the hydrothermal treatment consists condition, is prepared titanium dioxide nanoplate, and it is coated in minor matters shape TiO
2The nanometer stick array surface forms scattering layer, the nano-TiO of this multistage many structures
2The light anode is expected to have the excellent photoelectric performance.
Claims (10)
1. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode is characterized in that may further comprise the steps:
1) with after the electro-conductive glass cleaning, dry up for use;
2) utilize galvanostatic method in conductive glass surface deposition layer of ZnO nanometer stick array template;
3) with step 2) electro-conductive glass of preparation places and contains (NH
4)
2TiF
6Behind dipping in the boric acid mixed solution, take out, clean, obtain titanium dioxide nano-rod, dry the back calcining;
4) titanium dioxide nano-rod after will calcining is immersed in TiCl
4In the solution, place agitated reactor then, electro-conductive glass is leaned to the inwall in agitated reactor, in agitated reactor, add the mixed solution that contains HCl and butyl titanate, carry out hydro-thermal reaction, get dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode;
5) titanium dioxide nanoplate is synthetic: butyl titanate and HF are mixed, place agitated reactor, and airtight; After the hydro-thermal reaction, the gained white powder is taken out the centrifugation of washing back; The oven dry, products therefrom is placed ethanol solution, obtain the suspension of titanium dioxide nanoplate after; Rete at the product surface-coated layer of titanium dioxide nanometer sheet particle of step 4) gained promptly gets dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode.
2. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 1), and said electro-conductive glass adopts the FTO electro-conductive glass, and said electro-conductive glass is of a size of 1cm * 2cm; Said cleaning is that electro-conductive glass is put into acetone, deionized water, absolute ethyl alcohol ultrasonic cleaning successively, and the time of ultrasonic cleaning is 20～45min.
3. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1; It is characterized in that in step 2) in; The said galvanostatic method of utilizing is in FTO surface deposition layer of ZnO nanometer stick array template; Be to adopt two electrode systems, said two electrode systems are: electro-conductive glass is a work electrode, and the conduct of Pt electrode is to electrode; Electrolyte is by 1～10mM Zn (NO
3)
2With 1～10mM C
6H
12N
4Form, at the condition deposit 30～60min of constant-temperature constant-current, through for use after the washed with de-ionized water.
4. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 3), said (NH
4)
2TiF
6Concentration be 0.05～0.1M, the concentration of said boric acid is 0.15～0.5M.
5. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 3), and the time of said dipping is 3～5h; Said cleaning is to adopt washed with de-ionized water.
6. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 3), and the temperature of said calcining is 450 ℃, and the time of calcining is 2h, and the heating rate of calcining is 5 ℃/min.
7. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 4), said TiCl
4The concentration of solution is 0.1～0.7M.
8. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 4), and the time of said immersion is 30～60min; The quality percentage mark of said HCl solution is 10%～27%; The quality percentage mark of said butyl titanate is 1%～6%; The temperature of said hydro-thermal reaction is 150～180 ℃, and the time of hydro-thermal reaction is 1.5～20h.
9. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1 is characterized in that in step 5), and the concentration of said HF is 23%～46%; The temperature of said hydro-thermal reaction is 150～180 ℃, and the time of hydro-thermal reaction is 12～24h; Said washing is to use deionized water, sodium hydroxide solution, absolute ethanol washing successively, and the concentration of said sodium hydroxide solution is 0.1～1M.
10. the preparation method of dye sensibilization solar cell nanometer minor matters titanium dioxide photo anode as claimed in claim 1; It is characterized in that in step 5); The rete of said product surface-coated layer of titanium dioxide nanometer sheet particle at the step 4) gained is to utilize the rete of knife coating at the product surface-coated layer of titanium dioxide nanometer sheet particle of step 4) gained.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568850A (en) * | 2012-01-17 | 2012-07-11 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
| CN102836701A (en) * | 2012-07-23 | 2012-12-26 | 南京航空航天大学 | Preparation method of Si@TiO2 heterojunction nanocomposite |
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| CN114477278A (en) * | 2022-01-10 | 2022-05-13 | 山东科技大学 | Method for preparing black titanium oxide nanosheets by using simple ball milling technology |
| CN114544713A (en) * | 2020-11-24 | 2022-05-27 | 湖北大学 | Titanium dioxide rutile phase crystal face heterojunction gas-sensitive sensor and preparation method thereof |
| CN114758901A (en) * | 2022-04-06 | 2022-07-15 | 广西大学 | Preparation method of ZnO @ Ni/Co-ZIF energy storage film |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140957A (en) * | 2007-10-18 | 2008-03-12 | 清华大学 | Dye sensitization solar cell based on titanic oxide nano bar light scattering thin film electric pole and its preparing method |
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
-
2011
- 2011-06-03 CN CN 201110149652 patent/CN102306550B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
| CN101140957A (en) * | 2007-10-18 | 2008-03-12 | 清华大学 | Dye sensitization solar cell based on titanic oxide nano bar light scattering thin film electric pole and its preparing method |
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| CN102568850B (en) * | 2012-01-17 | 2015-01-07 | 上海联孚新能源科技集团有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
| CN102568850A (en) * | 2012-01-17 | 2012-07-11 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
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| CN113774426A (en) * | 2021-10-20 | 2021-12-10 | 中国科学技术大学 | Electrocatalyst and preparation method thereof |
| CN113774426B (en) * | 2021-10-20 | 2023-03-10 | 中国科学技术大学 | Electrocatalyst and preparation method thereof |
| CN114477278A (en) * | 2022-01-10 | 2022-05-13 | 山东科技大学 | Method for preparing black titanium oxide nanosheets by using simple ball milling technology |
| CN114758901A (en) * | 2022-04-06 | 2022-07-15 | 广西大学 | Preparation method of ZnO @ Ni/Co-ZIF energy storage film |
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| WO2024045408A1 (en) * | 2022-09-02 | 2024-03-07 | 深圳先进技术研究院 | Titanium homologous semiconductor heterojunction photoanode and preparation method therefor |
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