CN106952733A - Double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE and preparation method thereof, application - Google Patents
Double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE and preparation method thereof, application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/209—Light trapping arrangements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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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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- 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
Abstract
The invention discloses a kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE, it is characterised in that it includes composite luminescence layer and light scattering layer, and composite luminescence layer is by La (OH)3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide powder last doping are mixed, and light scattering layer is titanium dioxide bulky grain ball.La (OH) is doped with the double-deck photo-anode film of NEW TYPE OF COMPOSITE of the present invention, its composite luminescence layer3:Er3+/Yb3+Up-conversion luminescent material, green glow and red emission are converted to by the light in the range of near infrared band, enhance the absorption of light, and then enhance the photoelectric current that the light anode being sensitized with N719 dyestuffs, N3 dyestuffs, black dyestuff etc. constitutes device；The bulky grain ball of titanium dioxide adds the reflection of visible ray as scattering layer simultaneously, improve light utilization efficiency, photoelectric transformation efficiency in this, as the DSSC of light anode material is promoted to 9.2% by the result of two kinds of synergies, achieves significant progress.
Description
Technical field
The invention belongs to field of dye-sensitized solar cells, and in particular to a kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE and
Its preparation method, application.
Background technology
Developing rapidly for scientific and technological progress also brings a series of negative shadow while the living standard of the people is improved
Ring, crisis of resource, environmental pollution, population problem become society's problem urgently to be resolved hurrily, a kind of cleaning of exploitation, it is pollution-free, can
The energy of sustainable utilization becomes the emphasis of social each area research, and solar energy has above advantage concurrently, has been increasingly becoming researcher
The focus competitively developed.And solar cell is one of device of topmost utilization solar energy.Since 1991
Since team introduces DSSC (DSSCs), including DSSC, the quantum dot sensitized sun
Dye cell including energy battery, perovskite solar cell is wide concerned with its simple manufacture craft, relatively low cost.
DSSC is constituted by light anode, electrolyte and to electrode, and light anode is dye sensitization of solar
The skeleton of battery, not only carry electric transmission responsibility also act Dye Adsorption carrier effect, provided so as to prepare
The light anode material for having high-photoelectric transformation efficiency is one of forward position and focus of DSSC research.
At present apparently, researchers mainly by attempt novel semiconductor material, design light anode pattern and size with
And improve the performance of light anode in terms of optimization preparation technology, but these behaves to the raising of solar cell photoelectric efficiency simultaneously
It is not especially desirable.It is considered that when the light intensity of sunshine reaches maximum, being radiated the visible ray and near infrared light point on ground
44% and 40% are not accounted for, and the absorption spectrum ranges of dye molecule are narrower, the maximum absorption wavelength of general dyestuff is no more than
600nm, such as N3, N719, Z907.Even the DSSC of peak efficiency, its photoelectric transformation efficiency
Wavelength also only has 700nm in maximum magnitude, is not introduced into region of ultra-red, therefore sizable a part of spectrum is lost
.
The content of the invention
The technical problems to be solved by the invention are that there is provided one kind is new multiple for above shortcomings in the prior art
Double-deck photo-anode film and preparation method thereof, application are closed, on the one hand NEW TYPE OF COMPOSITE bilayer photo-anode film introduces conversion
Luminescent material, has widened spectral absorption scope；On the other hand add bulky grain ball adds light scattering, two kinds as scattering layer
Cooperative effect greatly strengthen light capture ability, finally improve the gross efficiency of DSSC.
The technical scheme that the present invention is used by solution the problem of set forth above for：
A kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE, it includes composite luminescence layer and light scattering layer, and composite luminescence layer is by La
(OH)3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide powder last doping are mixed, and light scattering layer is titanium dioxide bulky grain
Ball.
By such scheme, the light scattering layer thickness is about 5~12 μm, and the thickness of composite luminescence layer is 15~25 μm.
By such scheme, described La (OH)3:Er3+/Yb3+The mass ratio of upconversion luminescent powder and titania powder is
(0.5~8):(92~99.5).
By such scheme, the La (OH)3:Er3+/Yb3+In upconversion luminescent powder, La (OH)3With Er3+、Yb3+Quality
Than for 80：(1~10)：(10~19)；Its pattern is preferably nanometer rods, and the length of nanometer rods is about 20~70nm.The La
(OH)3:Er3+/Yb3+The absorbing wavelength of upconversion luminescent powder is 800~1500nm, and launch wavelength is 500~700nm.
By such scheme, the titanium dioxide bulky grain ball size is about 600~700nm, and rough surface.
By such scheme, the preferred titanium dioxide P25 powder of titania powder, size is 30~90nm；Or shape
Looks, size, crystalline phase and other close titania powders of P25.
By such scheme, the composite luminescence layer is located at lower floor, and light scattering layer is located at upper strata.
Present invention also offers a kind of preparation method of the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, comprise the following steps：
(1) by La (OH)3:Er3+/Yb3+Upconversion luminescent powder and titania powder are (0.5~8) according to mass ratio:
(92~99.5) mix, the first viscous syrup is prepared into after addition dispersant, levelling agent, pore-creating film forming agent；By first viscosity
Slurry is applied to conductive glass surface, in conductive glass surface formation composite luminescence layer after drying, annealing；
(2) the second viscosity slurry is prepared into after titanium dioxide bulky grain ball is mixed with dispersant, levelling agent, pore-creating film forming agent
Material, by the surface of composite luminescence layer obtained by the second viscous syrup application step (1), after drying, annealing, in compound hair
The surface of photosphere forms light scattering layer；
(3) composite luminescence layer and the light scattering layer for covering recombination luminescence layer surface formed in step (2), as new multiple
Close double-deck photo-anode film.
Further, the dispersant is absolute ethyl alcohol, isopropanol, butanol, acetone, glacial acetic acid, acetylacetone,2,4-pentanedione, but do not limit
In this, these dispersants can be used alone or with it is therein two or more be applied in combination.
Further, the levelling agent is the saturating alcohol of turpentine oil.
Further, the pore-creating film forming agent is fine using ethyl cellulose, methylcellulose, carboxycellulose, methylol
Dimension element or hydroxypropyl cellulose etc..
Further, the thickness of the first viscous syrup coating is 15~25um, the thickness of the second viscous syrup coating
For 5~12um.
Further, the electro-conductive glass uses FTO electro-conductive glass, its surface spin coating layer of titanium dioxide compacted zone.
Further, dispersant, levelling agent, pore-creating film forming agent are identical with step (1) in the step (2), and La
(OH)3:Er3+/Yb3+Both upconversion luminescent powder and titania powder common mass and dispersant, levelling agent, pore-creating film forming agent
Mass ratio be 1.5：39.5：(4.5~6)：(7.5~10.25), titanium dioxide bulky grain ball and dispersant, levelling agent, pore-creating
The mass ratio of film forming agent is 1.5:39.5：(4.5~6)：(7.5~10.25).
Further, the step (1) and annealing in step (2) are 400~500 DEG C of anneal 20~40min, 450
~550 DEG C of 20~40min of annealing.Wherein, heating rate is preferably 0.5~1.5 DEG C/min.
Present invention also offers a kind of DSSC containing above-mentioned NEW TYPE OF COMPOSITE photo-anode film.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the double-deck photo-anode film of NEW TYPE OF COMPOSITE of the present invention is doped with La (OH) in its composite luminescence layer3:Er3 +/Yb3+Up-conversion luminescent material, green glow and red emission are converted to by the light in the range of near infrared band, enhance the suction of light
Receive, and then enhance the photoelectric current that the light anode being sensitized with N719 dyestuffs, N3 dyestuffs, black dyestuff etc. constitutes device；Simultaneously
The bulky grain ball of titanium dioxide adds the reflection of visible ray as scattering layer, improves light utilization efficiency, two kinds of synergies
As a result the photoelectric transformation efficiency in this, as the DSSC of light anode material is promoted to 9.2%, than with La
(OH)3:Er3+/Yb3+Film prepared by upconversion luminescent powder doping P25 powder as light anode DSSC
Efficiency 6.3% improve 46%, than the efficiency that DSSC is assembled into using P25 films as light anode
5.4% improves 70%, achieves significant progress.
Second, the double-deck photo-anode film preparation technology of NEW TYPE OF COMPOSITE of the present invention is simple, easily operated, effect is notable,
Environment-friendly, cost economy, is that futurity industry, large-scale production perform place mat.
3rd, the double-deck photo-anode film of the NEW TYPE OF COMPOSITE, La (OH) in its composite luminescence layer3:Er3+/Yb3+Upper conversion hair
The doping of light powder can produce transformation within the specific limits, and proportion on probation is larger, and La (OH)3:Er3+/
Yb3+Upconversion luminescent powder light absorption range is broad, can improve the utilization rate near infrared region light, so as to improve the photoelectricity of device
Performance.
Brief description of the drawings
Fig. 1 is La (OH) in the up-conversion luminescent material used in the embodiment of the present invention3X-ray diffractogram.
Fig. 2 is the up-conversion luminescent material La (OH) used in the embodiment of the present invention3:Er3+/Yb3+Transmission electron microscope picture.
Fig. 3 is the up-conversion luminescent material La (OH) used in the embodiment of the present invention3:Er3+/Yb3+Launching light spectrogram.
Fig. 4 is the X-ray diffractogram of the titanium dioxide bulky grain ball used in the embodiment of the present invention.
Fig. 5 is the ESEM schematic diagram of the titanium dioxide bulky grain ball used in the embodiment of the present invention.
Fig. 6 is the structure and principle schematic of NEW TYPE OF COMPOSITE bilayer film.
Fig. 7 is the cross-sectional scans electron microscope of NEW TYPE OF COMPOSITE duplicature prepared by the embodiment of the present invention 1.
Fig. 8 is the embodiment of the present invention 1, comparative example 1, three kinds of different photo-anode film dye sensitization sun of the preparation of comparative example 2
The diffusing reflection rate curve of energy battery.
Fig. 9 is that the dyestuff that three kinds of different films prepared by the embodiment of the present invention 1, comparative example 1, comparative example 2 are assembled into is quick
Change the J-V curves of solar cell.
Embodiment
For a better understanding of the present invention, with reference to embodiment and the accompanying drawing content that the present invention is furture elucidated, but this
Invention is not limited solely to the following examples.
A kind of up-conversion luminescent material La (OH) is provided in the present invention3:Er3+/Yb3+For subsequent embodiment, its preparation side
Method comprises the following steps：
1) the 1.5ml rare earth aqueous solutions configured are added in 20ml deionized waters, the total mole number of its contained solute is
(mol ratio that solute includes each material is n (La (NO to 0.3mmol3)3):n(Yb(NO3)3):n(Er(NO3)3)=80:18:
2) 15min, is stirred, 1.2ml NaF solution is then continuously added in above-mentioned solution, and (substance withdrawl syndrome is 1molL-1), it is acute
Strong stirring 30min, obtains mixed solution；
2) 1molL is used-1NaOH solution to adjust the pH of above-mentioned mixed solution be 14, be then transferred to 100ml's
180 DEG C of hydro-thermal reaction 24h in the reactor of polytetrafluoroethylene (PTFE)；
3) after hydro-thermal reaction terminates, products therefrom solution is cooled to room temperature, removes and deionized water and second are used after supernatant
Alcohol washs solid product three times and centrifuged respectively, and then in drying 24h at 80 DEG C, then anneal 2h at 550 DEG C, obtains
The product of white powder, i.e. upconversion luminescent powder La (OH)3:Er3+/Yb3+。
Pass through Fig. 1 and Fig. 2：The upconversion luminescent powder of above-mentioned preparation is Er3+/Yb3+The La (OH) of codope3, its shape
Looks are nano bar-shape, and length is 20~70nm；As shown in Figure 3：The upconversion luminescent powder have very strong feux rouges (wavelength 625~
670nm) launch with green glow (510~570nm of wavelength).
In following embodiments, the titanium dioxide P25 powder, size is 30~90nm.
In following embodiments, FTO conductive glass surface spin coatings have titanium dioxide dense layer slurry, and dense layer thickness is about 40
~80nm, compacted zone slurry is bought in Wuhan lattice company.
Embodiment 1
As shown in fig. 7, a kind of new composite double layer photo-anode film, it includes composite luminescence layer and light scattering layer, multiple
Luminescent layer is closed by La (OH)3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide P25 powder are according to mass ratio 3:97 are composited,
Light scattering layer is titanium dioxide bulky grain ball；Wherein, the thickness of the composite luminescence layer is 18.3 μm, and scattering layer thickness is
8.91um。
Titanium dioxide bulky grain ball used by the present embodiment, its preparation method comprises the following steps：
1) the pure tetrabutyl titanate of 1mL traditional Chinese medicines analysis and the pure ethylene glycol of 25mL traditional Chinese medicines analysis are sufficiently stirred for 12h and are well mixed,
Then above-mentioned gained mixed solution is added in the beaker for filling the analytically pure acetone of 90mL traditional Chinese medicines, after stirring 0.5h, then it is quiet
Put aging 48h；
2) solution after aging will be stood and removes supernatant, then washed three times, be put into respectively with deionized water and ethanol
80 DEG C of vacuum drying 6h, obtain white solid in vacuum drying chamber；
3) white solid is transferred in crucible, it is 3 DEG C/min to be put into Muffle furnace according to heating rate, is warming up to 500
DEG C annealing 60min processing, obtain white powder.As shown in Figure 4：The white powder is titanium dioxide, major part crystalline phase
For Anatase；As shown in figure 5, the white titania powder is large granular spherical, particle size is about 600~650nm.
The preparation method of the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, comprises the following steps：
(1) by the La (OH) of above-mentioned preparation3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide P25 powder shine mass ratio 3:
97 are doped mixing, obtain mixture；Gained mixture 1.5g is weighed to be put into 100ml small beaker, and it is scattered with 50mL
Agent (absolute ethyl alcohol), 5.0g levelling agents (the saturating alcohol of turpentine oil), 8.25g pore-creating film forming agent (ethyl cellulose) are sufficiently mixed agitated
Heating evaporates into ethanol to be prepared into the first viscous syrup afterwards to a certain degree；
First viscous syrup is applied to the surface for the FTO electro-conductive glass for having been spun on compacted zone, coating thickness is used
It is the thickness of two layers of adhesive tape that 3M adhesive tapes, which control it, is then dried at room temperature for after 10min, is put into Muffle furnace according to heating rate
450 DEG C of annealing 30min are warming up to for 1 DEG C/min, then are warming up to 500 DEG C of annealing 30min, form multiple in FTO conductive glass surfaces
Close luminescent layer；
(2) by the above-mentioned titanium dioxide bulky grain powder of 1.5g and 50mL dispersants (absolute ethyl alcohol), 5.0g levelling agent (turpentines
Oily alcohol thoroughly), 8.25g pore-creating film forming agent (ethyl cellulose) is sufficiently mixed agitated heating and evaporates into ethanol and make afterwards to a certain degree
It is standby into the second viscous syrup；Second viscous syrup is coated on to the surface of composite luminescence layer obtained by step (1), the thickness of coating
Thickness for one layer tape is controlled by 3M adhesive tapes, is then dried at room temperature for after 10min, is put into Muffle furnace according to heating
Speed is warming up to 450 DEG C of annealing 30min for 1 DEG C/min, then is warming up to 500 DEG C of annealing 30min, in the surface shape of composite luminescence layer
Into scattering layer, that is, obtain the double-deck photo-anode film of the NEW TYPE OF COMPOSITE.
The double-deck photo-anode film of NEW TYPE OF COMPOSITE obtained by the present embodiment is by the composite luminescence layer of lower floor and the light scattering layer on upper strata
Composition, as shown in fig. 7, the thickness of composite luminescence layer is 18.3um, the thickness of light scattering layer is 8.91um, this double membrane structure
Light anode be assembled into the photoelectric transformation efficiency that device is finally obtained 9.2%.
Comparative example 1
Difference with embodiment 1 is：The first viscous syrup coating coating thickness is 3 layers of adhesive tape in step (1)
Thickness；Omit step (2).
Comparative example 2
Difference with embodiment 1 is：By 1.5g business P25 powder and 50mL dispersants (anhydrous second in step (1)
Alcohol), 5.0g levelling agents (the saturating alcohol of turpentine oil), 8.25g pore-creating film forming agent (ethyl cellulose) are sufficiently mixed agitated heating makes second
Alcohol is evaporated into is prepared into the first viscous syrup afterwards to a certain degree, and it is the thickness of 3 layers of adhesive tape that its coating thickness, which controls it with 3M adhesive tapes,；
Omit step (2).
The present embodiment and comparative example 1, the gained photo-anode film of comparative example 2 characterize obtaining result as shown in Figure 8, will
It is soaked after dyestuff, is characterized after avoid light place 24h, draws the result such as Fig. 9, and the photoelectricity that embodiment 1 obtains 9.2% turns
Efficiency is changed, comparative example 1 obtains 6.3% photoelectric transformation efficiency, and comparative example 2 obtains 5.4% photoelectric transformation efficiency, and this fills
Divide and demonstrate the superior photoelectric properties of the double-deck photo-anode film of NEW TYPE OF COMPOSITE of the present invention.Gained double-layer compound film conduct of the invention
The photo-anode film of DSSC, on the one hand the upper transformation based on upconversion luminescent powder is by spectral absorption scope
Widen to near-infrared, scattering layer is on the other hand introduced according to Mie scattering theories, when the particle diameter of particle and the wavelength of light are suitable
When, multiple reflections, refraction, diffraction and absorption, the dye molecule pair of increase absorption in the film can occur inside film for light
The particle size of material is lucky in the range of visible light wave in the utilization rate of light, the upper layer film of duplicature, therefore, double-deck in Fig. 8
The reflectivity highest of film is to be based on this theory.
Embodiment 2
Present embodiments provide a kind of preparation method for preparing the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, including following step
Suddenly：
Titanium dioxide bulky grain ball used by the present embodiment, its preparation method comprises the following steps：
A kind of new composite double layer photo-anode film, it includes composite luminescence layer and scattering layer, and composite luminescence layer is by La
(OH)3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide P25 powder are respectively 1 according to mass ratio：99、2：98、4：96、5：
95、6：94 doped and compoundeds are formed, and scattering layer is titanium dioxide bulky grain ball.
Titanium dioxide bulky grain ball used by the present embodiment, its preparation method is same as Example 1.
The preparation method of the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, comprises the following steps：
(1) by the La (OH) of above-mentioned preparation3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide P25 powder shine quality score
Wei 1：99、2：98、4：96、5：95、6：94 are doped mixing, obtain mixture；Gained mixture 1.5g is weighed respectively to put
In the small beaker for entering 5 100ml, numbering 1,2,3,4,5, and it is (loose with 50mL dispersants (absolute ethyl alcohol), 5.0g levelling agents respectively
The saturating alcohol of fuel-economizing), 8.25g pore-creating film forming agent (ethyl cellulose) is sufficiently mixed agitated heating makes after ethanol evaporates into a certain degree
It is prepared into 5 group of first viscous syrup；
5 group of first viscous syrup is respectively coated to the surface for the FTO electro-conductive glass for having been spun on compacted zone, is coated with
It is the thickness of two layers of adhesive tape that thickness, which controls it with 3M adhesive tapes, is then dried at room temperature for after 10min, is put into Muffle furnace according to liter
Warm speed is warming up to 450 DEG C of annealing 30min for 1 DEG C/min, then is warming up to 500 DEG C of annealing 30min, in FTO conductive glass surfaces
Form composite luminescence layer；
(2) by the above-mentioned titanium dioxide bulky grain powder of 1.5g and 50mL dispersants (absolute ethyl alcohol), 5.0g levelling agent (turpentines
Oily alcohol thoroughly), 8.25g pore-creating film forming agent (ethyl cellulose) is sufficiently mixed agitated heating and evaporates into ethanol and make afterwards to a certain degree
It is standby into the second viscous syrup；Second viscous syrup is coated on to the surface of composite luminescence layer obtained by step (1), the thickness of coating
Thickness for one layer tape is controlled by 3M adhesive tapes, is then dried at room temperature for after 10min, is put into Muffle furnace according to heating
Speed is warming up to 450 DEG C of annealing 30min for 1 DEG C/min, then is warming up to 500 DEG C of annealing 30min, in the surface shape of composite luminescence layer
Into scattering layer, that is, obtain the double-deck photo-anode film of the NEW TYPE OF COMPOSITE.
5 groups of double-deck photo-anode films in embodiment 2 are assembled into device, are finally obtained 4%~6% opto-electronic conversion effect
Rate.
Embodiment 3
Present embodiments provide a kind of preparation method for preparing the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, including following step
Suddenly：
Titanium dioxide bulky grain ball used by the present embodiment, its preparation method comprises the following steps：
1) the pure butyl titanate of 1mL traditional Chinese medicines analysis and the pure ethylene glycol of 25mL traditional Chinese medicines analysis are sufficiently stirred for 12h and are well mixed,
Then above-mentioned gained mixed solution is added in the beaker for filling the analytically pure acetone of 110mL traditional Chinese medicines, after stirring 0.5h, then it is quiet
Put aging 48h；
2) solution after aging will be stood and removes supernatant, then washed three times, be put into respectively with deionized water and ethanol
80 DEG C of vacuum drying 6h, obtain white solid in vacuum drying chamber；
3) white solid is transferred in crucible, it is 3 DEG C/min to be put into Muffle furnace according to heating rate, is warming up to 500
DEG C annealing 60min processing, obtains white powder, powder is ellipse, particle size is 750~800nm.
The preparation method of the double-deck photo-anode film of above-mentioned NEW TYPE OF COMPOSITE, comprises the following steps：
(1) by the La (OH) of above-mentioned preparation3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide P25 powder shine mass ratio 3:
97 are doped mixing, obtain mixture；Gained mixture 1.5g is weighed to be put into 100ml small beaker, and it is scattered with 50mL
Agent (absolute ethyl alcohol), 5.0g levelling agents (the saturating alcohol of turpentine oil), 8.25g pore-creating film forming agent (ethyl cellulose) are sufficiently mixed agitated
Heating evaporates into ethanol to be prepared into the first viscous syrup afterwards to a certain degree；
First viscous syrup is applied to the surface for the FTO electro-conductive glass for having been spun on compacted zone, coating thickness is used
It is the thickness of two layers of adhesive tape that 3M adhesive tapes, which control it, is then dried at room temperature for after 10min, is put into Muffle furnace according to heating rate
450 DEG C of annealing 30min are warming up to for 1 DEG C/min, then are warming up to 500 DEG C of annealing 30min, form multiple in FTO conductive glass surfaces
Close luminescent layer；
(2) by the above-mentioned titanium dioxide bulky grain powder of 1.5g and 50mL dispersants (absolute ethyl alcohol), 5.0g levelling agent (turpentines
Oily alcohol thoroughly), 8.25g pore-creating film forming agent (ethyl cellulose) is sufficiently mixed agitated heating and evaporates into ethanol and make afterwards to a certain degree
It is standby into the second viscous syrup；Second viscous syrup is coated on to the surface of composite luminescence layer obtained by step (1), the thickness of coating
Thickness for one layer tape is controlled by 3M adhesive tapes, is then dried at room temperature for after 10min, is put into Muffle furnace according to heating
Speed is warming up to 450 DEG C of annealing 30min for 1 DEG C/min, then is warming up to 500 DEG C of annealing 30min, in the surface shape of composite luminescence layer
Into scattering layer, that is, obtain the double-deck photo-anode film of the NEW TYPE OF COMPOSITE.
Composite double layer photo-anode film prepared by embodiment 3, is assembled into the opto-electronic conversion effect that device is finally obtained 6.0%
Rate.
The above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE, it is characterised in that it includes composite luminescence layer and light scattering layer, is combined hair
Photosphere is by La (OH)3:Er3+/Yb3+Upconversion luminescent powder and titanium dioxide powder last doping are mixed, and light scattering layer is titanium dioxide
Titanium bulky grain ball.
2. a kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE according to claim 1, it is characterised in that the light scattering thickness
Spend for 5~12 μm, the thickness of composite luminescence layer is 15~25 μm, and the composite luminescence layer is located at light scattering layer lower floor.
3. a kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE according to claim 1, it is characterised in that described La (OH)3:
Er3+/Yb3+The mass ratio of upconversion luminescent powder and titania powder is (0.5~8):(92~99.5).
4. a kind of double-deck photo-anode film of NEW TYPE OF COMPOSITE according to claim 1, it is characterised in that the La (OH)3:Er3 +/Yb3+In upconversion luminescent powder, La (OH)3With Er3+、Yb3+Mass ratio be 80：(1~10)：(10~19), pattern is nanometer
Rod, and the length of nanometer rods is about 20~70nm.
5. the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE according to claim 1, it is characterised in that the titanium dioxide is big
Particle ball size is 600~700nm, and principal crystalline phase is anatase；The titania powder is titanium dioxide P25 powder.
6. the preparation method of the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE, it is characterised in that it comprises the following steps：
(1) by La (OH)3:Er3+/Yb3+Upconversion luminescent powder and titania powder are (0.5~8) according to mass ratio：(92~
99.5) mix, the first viscous syrup is prepared into after addition dispersant, levelling agent, pore-creating film forming agent；First viscous syrup is applied
Cloth is to conductive glass surface, in conductive glass surface formation composite luminescence layer after drying, annealing；
(2) the second viscous syrup is prepared into after titanium dioxide bulky grain ball is mixed with dispersant, levelling agent, pore-creating film forming agent,
By the surface of composite luminescence layer obtained by the second viscous syrup application step (1), after drying, annealing, in recombination luminescence
The surface of layer forms light scattering layer；
(3) composite luminescence layer and the light scattering layer for covering recombination luminescence layer surface formed in step (2), as NEW TYPE OF COMPOSITE are double
Layer photo-anode film.
7. the preparation method of the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE according to claim 6, it is characterised in that described
Dispersant is selected from the one or more in absolute ethyl alcohol, isopropanol, butanol, acetone, glacial acetic acid, acetylacetone,2,4-pentanedione, the levelling agent
For the saturating alcohol of turpentine oil, the pore-creating film forming agent is selected from ethyl cellulose, methylcellulose, carboxycellulose, hydroxymethyl cellulose
Or hydroxypropyl cellulose.
8. the preparation method of the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE according to claim 6, it is characterised in that described
La(OH)3:Er3+/Yb3+Both upconversion luminescent powder and titania powder common mass and dispersant, levelling agent, pore-creating film forming
The mass ratio of agent is (1~2)：(35~45)：(4.5~6)：(7.5~10.25), titanium dioxide bulky grain ball and dispersant, stream
Flat agent, the mass ratio of pore-creating film forming agent are (1~2)：(35~45)：(4.5~6)：(7.5~10.25).
9. the preparation method of the double-deck photo-anode film of a kind of NEW TYPE OF COMPOSITE according to claim 6, it is characterised in that described
Step (1) is 400~500 DEG C of annealing 20~40min, 450~550 DEG C of 20~40min of annealing with annealing in step (2).
10. a kind of DSSC for including NEW TYPE OF COMPOSITE photo-anode film described in claim 1.
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