CN101030607A - Sensitized dye solar battery light anode and its production - Google Patents
Sensitized dye solar battery light anode and its production Download PDFInfo
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- CN101030607A CN101030607A CNA2007100905564A CN200710090556A CN101030607A CN 101030607 A CN101030607 A CN 101030607A CN A2007100905564 A CNA2007100905564 A CN A2007100905564A CN 200710090556 A CN200710090556 A CN 200710090556A CN 101030607 A CN101030607 A CN 101030607A
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- dye
- solar cell
- sensitized solar
- metallic compound
- dyestuff
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- 238000004519 manufacturing process Methods 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 4
- 230000008313 sensitization Effects 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 34
- 229910000765 intermetallic Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 125000005341 metaphosphate group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 230000005622 photoelectricity Effects 0.000 abstract 1
- 238000005036 potential barrier Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 13
- 239000012528 membrane Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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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- Photovoltaic Devices (AREA)
Abstract
The invention is concerned with the nanometer porous titanium dioxide lighting anode and the manufacture method that is in the dye sensitization solar cell material field. It is: prepares the TiO2 nanometer porous thin film on the conductive basement; uses the metal compound to process surface modification then absorbs the dye; forms the surface potential barrier, improves the energy level of the semiconductor, and controls the surface state by the modification of the metal compound layer. The invention can improve the photoelectricity transformation capability and the efficiency of the cell, the efficiency can increase 10%-20%.
Description
Technical field
The present invention relates to DSSC material field, relate in particular to a kind of nano porous titanium dioxide light anode and preparation method thereof.
Background technology
Along with the development of World Economics and the increase of population, increasing to the demand of the energy.Since last century, broke out energy crisis the seventies, the utilization of regenerative resources such as solar energy, wind energy, water energy has been obtained significant progress.And compare with other energy, solar energy has incomparable advantage.Compare with fossil energy, solar energy is inexhaustible; And environmental sound, can not produce a large amount of pernicious gases, can not destroy the heat balance of the earth, be favourable to the ecological protection of keeping the earth.Compare with nuclear energy, utilize simple, safe in utilization.Can compare with wind energy, water, not limited by geographical conditions, can use on a large scale on a large scale.
From 1954, the Chapin of Bell Laboratory developed efficient and has reached since 6% the monocrystalline silicon photocell, and the kind of solar cell and efficient constantly are improved and develop.In the whole evolution of solar cell, the battery that various different structures successively occurred, as Schottky (MS) battery, MIS battery, MINP battery, heterojunction battery etc., the material of use has monocrystalline silicon, amorphous silicon, copper indium diselenide (CIS), cadmium telluride (CdTe), GaAs (GaAs) etc.Because the absorption of light and the transmission of charge carrier are carried out synchronously in the semi-conductor cell, in order to prevent the compound again of electronics-hole, the material of battery must possess high-purity, and there is not fault of construction, therefore, serious photoetch and expensive price make the application of this battery be subjected to certain restriction.
Two ten years from early seventies to the nineties, very active always with the research of organic dye sensitized wide bandgap semiconductor.But the research of early stage this respect mainly concentrates on the plate electrode, can only be at the dye molecule of electrode surface absorption monolayer, because the efficient of dye molecule absorption sunlight is very low, photoelectric conversion efficiency can't improve always, all the time below 1%, reach realistic scale far away.Up to 1991, the Gr tzel of Lausanne, SUI higher technical school
People such as professor have proposed a kind of photovoltaic cell---DSSC of novel use carboxylic acid bipyridyl ruthenium (II) complex sensitized porous titanium dioxide nanostructure light anode, for the development of photoelectrochemical cell brings revolutionary innovation.Its photoelectric conversion efficiency has been issued to 7.1% in the irradiation of AM1.5 solar simulated, and its price has only the part of conventional semiconductors solar cell.
The battery of prior art is mainly formed by transparent conduction base sheet, porous nano titanium deoxid film, sensitizing dyestuff, electrolyte solution with to electrode.When energy is lower than the semiconductor energy gap, but the incident illumination that equals the dye molecule characteristic absorption wavelength is on electrode the time, be adsorbed on electronics induced transition in the dye molecule of electrode surface to excitation state, be injected in the titanium dioxide conduction band then rapidly, and be enriched to conductive substrates, and flow to electrode by external circuit, form electric current.And after electronics injected, dye molecule self changed oxidation state into, the electron donor in the oxidization electrolysis matter solution subsequently, and self-recovery makes dye molecule obtain regenerating for going back ortho states.Oxidized electrolyte diffusion is conducted the electron reduction of coming at electrode surface from the light anode, thereby is finished an Optical Electro-Chemistry reaction cycle to electrode.In whole process, the total state of each reaction species is constant, and luminous energy is converted into electric energy.
The principal element that influences the DSSC photoelectric conversion efficiency has: the light anode is to the absorption efficiency of sunlight, the injection efficiency of electronics, the collection efficiency of electronics and electronics reverse compound etc.The light anode is big more to the absorption of sunlight, and the injection efficiency of electronics and collection efficiency are high more, and electron back is to compound more little, and the photoelectric conversion efficiency of battery is high more.Wherein the light anode is to the absorption of light, the injection of electronics, and the reverse compound grade of electronics all concentrates on TiO
2On/dyestuff/electrolyte interface, therefore, research TiO
2Just seem particularly important with dyestuff and electrolytical interface.A large amount of studies show that at present, the principal element of restriction solar cell photoelectric conversion efficiency is that open circuit voltage is lower, and electron back causes battery open circuit voltage decline to reach 0.3V to recombination energy.Therefore, if can reduce TiO
2With electron back on dyestuff and the electrolyte interface to compound, thereby the open circuit voltage that will improve battery greatly improves the opto-electronic conversion performance of battery.On the other hand, the present dyestuff (N3 and N719) that generally uses is by carboxyl and TiO
2Surface Cheng Jian; If by the modification of metallic compound, can strengthen TiO
2The alkalescence on surface then can increase the dyestuff adsorbance, thereby makes the light anode increase the absorption of light, might improve the short circuit current of battery.Therefore, utilize metallic compound to modify TiO
2The light anode can improve the photoelectric conversion efficiency of solar cell.
Summary of the invention
The object of the present invention is to provide a kind of light anode of DSSC, improve the opto-electronic conversion performance of battery, improve the photoelectric conversion efficiency of battery.
Another object of the present invention is to provide a kind of method for preparing above-mentioned dye-sensitized solar cell anode.
Dye-sensitized solar cell anode provided by the invention is substrate with the broad stopband nano-porous film, modifies the layer of metal compound at this substrate surface, and then absorbing dye composition light anode, and the metal ion of metallic compound is selected from Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of.
Described broad stopband nano-porous film is the nano titania perforated membrane; Dyestuff is that suitable-two (thiocyanate radical)-two (4,4-dicarboxylic acids-2,2-bipyridine) close ruthenium (being called for short the N3 dyestuff) or its derivative N719 dyestuff.
Metallic compound can be for being selected from Pb
2+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of oxide of ion, hydroxide, sulfide, carbonate, sulfate, phosphate, phosphite, hypophosphites or metaphosphate.
All constitute the decorative layer of substrate in the prior art, and the present invention adopts the decorative layer of metallic compound formation substrate, for the photoelectric conversion rate that improves battery opens up a new way with metal ion.
The invention provides the method for preparing dye-sensitized solar cell anode according to following step:
A) the broad stopband nano porous semiconductor film of preparation metallic compound modification
With particle size is the 2-100 nanometer, and the broad stopband nano porous semiconductor film of 1-50 micron thickness soaked in the metal ion solution of 0.005-1 mol 1 second to 12 hours, and taking-up is dried, and is placed in the air 0.5-6 hour; Obtain the nano-porous film that metallic compound is modified; Metal ion in the metallic compound is selected from Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of;
B) the broad stopband nano porous semiconductor film of sensitization metallic compound modification
The broad stopband nano-porous film that the resulting metallic compound of a step is modified is 10
-5-10
-3Soaked 30 minutes-24 hours in the organic solvent of mol dyestuff.
Method preferably, its step comprises:
A) nano-porous film of preparation metallic compound modification
With particle size 2-100 nanometer, the broad stopband nano porous semiconductor film of 1-50 micron thickness soaked in the metal compound solution of 0.005-1 mol 1 second to 12 hours, and taking-up is dried, and was placed in the air 0.5-6 hour; Metal ion in the metallic compound is selected from Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of;
B) sintering of metallic compound decorated nanometer porous membrane
With the resulting broad stopband of a step nano-porous film 100-600 ℃ of following sintering 5 minutes-12 hours;
C) nano-porous film of sensitization metallic compound modification
With the resulting broad stopband of b step nano-porous film 10
-5-10
-3Soaked 30 minutes-24 hours in the organic solvent of mol dyestuff.
Broad stopband nano porous semiconductor film in the said method is a titanium dioxide film, is that preparation is suprabasil at transparent conducting glass, and transparent conducting glass can be the tin ash glass of indium doping or the tin ash glass that fluorine mixes; Dyestuff wherein can be N3 dyestuff or N719 dyestuff; Metal compound solution can be the aqueous solution or non-aqueous solution.
In the said method, described metallic compound is for being selected from Pb
2+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of oxide of ion, hydroxide, sulfide, carbonate, sulfate, phosphate, phosphite, hypophosphites, metaphosphate.
Beneficial effect of the present invention is:
After battery of the present invention is modified by metal compound layer, TiO
2The dyestuff of surface adsorption increases, reverse compound the reducing of battery, and open circuit voltage improves, and opto-electronic conversion performance of the present invention is than the generally raising 10-20% that does not modify by metal compound layer.
Description of drawings
Fig. 1: the solar battery structure schematic diagram of electrode of the present invention; Wherein, 1, electro-conductive glass light anode; 2, titanium dioxide and dye coating; 3, metallic compound decorative layer; 4, electrolyte; 5, platinum plating layer; 6, electro-conductive glass photocathode; 7, titanium dioxide; 8, dyestuff; 9, metallic compound.
Fig. 2: BaCO
3Modify TiO
2Absorption spectrum; Wherein, solid line represents to adsorb the TiO behind the N3
2Film, dotted line represent to adsorb the BaCO behind the N3
3The TiO that modifies
2Film; Ordinate is represented absorptance (Absorbance), and abscissa is represented wavelength (Wavelength).
Fig. 3: BaCO
3Modify TiO
2Dark current; Wherein solid line is represented the dark current of normal battery, and dotted line is represented TiO
2Through BaCO
3The dark current of the battery of modifying; Ordinate is represented electric current (Current), and abscissa is represented voltage (Potential).
Embodiment
The present invention is further illustrated with embodiment, be of value to further understanding of the present invention, but embodiment do not limit protection scope of the present invention, and protection scope of the present invention is decided by claims.
Present embodiment is the experiment of not modifying through metal compound layer.
With a TiO
2Perforated membrane is at 3.5*10
-4Soak in the N3 ethanolic solution of mol/L after 12 hours, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.56V, short circuit current is 11.1mA/cm
2, fill factor, curve factor 56.1%, total photoelectric conversion efficiency 3.49%.
Embodiment 2
With TiO
2Perforated membrane is at the Ba of 0.05M (OH)
2Immersion with drying behind the deionized water rinsing, was placed 4 hours in air after 10 minutes in the aqueous solution.450 ℃ of following sintering were lowered the temperature after 30 minutes, at 3.5*10
-4Soak in the N3 ethanolic solution of mol/L after 12 hours, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.64V, short circuit current is 10.4mA/cm
2, fill factor, curve factor 65.1%, total photoelectric conversion efficiency 4.33%.
Embodiment 3
With TiO
2Perforated membrane is at the Sr of 0.005M (OH)
2Immersion with drying behind the deionized water rinsing, was placed 6 hours in air after 10 minutes in the aqueous solution.450 ℃ of following sintering were lowered the temperature after 30 minutes, at 3.5*10
-4Soak in the N719 ethanolic solution of mol/L after 12 hours, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.61V, short circuit current is 10.6mA/cm
2, fill factor, curve factor 60.5%, total photoelectric conversion efficiency 3.91%.
Embodiment 4
With TiO
2Perforated membrane is at the Ca of 0.02M (OH)
2Soak in the aqueous solution after 1 second with drying behind the deionized water rinsing, in air, placed 0.5 hour.450 ℃ of following sintering were lowered the temperature after 30 minutes, at 3.5*10
-4Soak in the N3 ethanolic solution of mol/L after 12 hours, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.60V, short circuit current is 10.3mA/cm
2, fill factor, curve factor 62.7%, total photoelectric conversion efficiency 3.87%.
Embodiment 5
With TiO
2Perforated membrane is at the Sr of 0.02M (OH)
2Immersion with drying behind the deionized water rinsing, was placed 2 hours in air after 10 minutes in the aqueous solution.100 ℃ of following sintering were lowered the temperature after 12 hours, at 3.5*10
-5Soak in the N3 ethanolic solution of mol/L after 30 minutes, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.60V, short circuit current is 10.1mA/cm
2, fill factor, curve factor 60.5%, total photoelectric conversion efficiency 3.67%.
Embodiment 6
With TiO
2Perforated membrane is at the Ba of 1M (OH)
2Immersion with drying behind the deionized water rinsing, was placed 4 hours in air after 12 hours in the aqueous solution.600 ℃ of following sintering were lowered the temperature after 1 hour, at 3.5*10
-3Soak in the N719 ethanolic solution of mo1/L after 24 hours, take out with the absolute ethyl alcohol flushing, dry, adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.58V, short circuit current is 11.6mA/cm
2, fill factor, curve factor 61.5%, total photoelectric conversion efficiency 4.14%.
Embodiment 7
With TiO
2Perforated membrane is at the Ca of 0.02M (OH)
2Immersion with drying behind the deionized water rinsing, was placed 4 hours in air after 10 minutes in the aqueous solution.450 ℃ of following sintering were lowered the temperature after 30 minutes, at 3.5*10
-4Soak in the N3 ethanolic solution of mol/L after 12 hours, take out with the absolute ethyl alcohol flushing, dry, adopt liquid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2White light under, the open circuit voltage of the battery that records is 0.67V, short circuit current is 19.3mA/cm
2, fill factor, curve factor 65.7%, total photoelectric conversion efficiency 8.50%.
Claims (11)
1, a kind of dye-sensitized solar cell anode, with the broad stopband nano porous semiconductor film is substrate, it is characterized in that this substrate surface modifies the layer of metal compound, absorbing dye again on metallic compound then, the metal ion in the described metallic compound is selected from Pb
2+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+In wherein a kind of.
2, dye-sensitized solar cell anode as claimed in claim 1 is characterized in that described broad stopband nano porous semiconductor film is a titanium dioxide film.
3, dye-sensitized solar cell anode as claimed in claim 1 is characterized in that described metallic compound is for being selected from Pb
2+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of oxide of ion, hydroxide, sulfide, carbonate, sulfate, phosphate, phosphite, hypophosphites or metaphosphate.
4, dye-sensitized solar cell anode as claimed in claim 1 is characterized in that described dyestuff is N3 dyestuff or N719 dyestuff.
5, a kind of method for preparing nanoporous dye-sensitized solar cell anode as claimed in claim 1, its step comprises:
A) the broad stopband nano porous semiconductor film of preparation metallic compound modification
With particle size is the 2-100 nanometer, the broad stopband nano porous semiconductor film of 1-50 micron thickness soaked in the metal compound solution of 0.005-1 mol 1 second to 12 hours, taking-up is dried, and is positioned in the air, obtains the broad stopband nano porous semiconductor film that metallic compound is modified; Metal ion in the described metallic compound is selected from Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of;
B) the broad stopband nano porous semiconductor film of sensitization metallic compound modification
The broad stopband nano porous semiconductor film that the resulting metallic compound of a step is modified is 10
-5-10
-3Soaked 30 minutes-24 hours in the organic solvent of mol dyestuff.
6, the method for preparing dye-sensitized solar cell anode as claimed in claim 5 is characterized in that broad stopband nano porous semiconductor film that the metallic compound of a step gained is modified is at 100-600 ℃ of following sintering after 5 minutes-12 hours, 10
-5-10
-3Soaked 30 minutes-24 hours in the organic solvent of mol dyestuff.
7, as claim 5 or the 6 described methods that prepare dye-sensitized solar cell anode, it is characterized in that will soak at metal compound solution the broad stopband nano porous semiconductor film take out dry after, be positioned in the air 0.5-6 hour.
8,, it is characterized in that described broad stopband nano porous semiconductor film is a titanium dioxide film as claim 5 or the 6 described methods that prepare dye-sensitized solar cell anode.
9,, it is characterized in that described dyestuff is N3 dyestuff or N719 dyestuff as claim 5 or the 6 described methods that prepare dye-sensitized solar cell anode.
10,, it is characterized in that described metal compound solution can be the aqueous solution or non-aqueous solution as claim 5 or the 6 described methods that prepare dye-sensitized solar cell anode.
11, as claim 5 or the 6 described methods that prepare dye-sensitized solar cell anode, it is characterized in that described metallic compound is for being selected from Pb
2+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zr
4+, Nb
5+Wherein a kind of oxide of ion, hydroxide, sulfide, carbonate, sulfate, phosphate, phosphite, hypophosphites, metaphosphate.
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CN102280264A (en) * | 2011-05-20 | 2011-12-14 | 常州有则科技有限公司 | Titanium/strontium covered nanocrystalline titanium dioxide film for dye-sensitized solar cell and preparation method thereof |
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CN102280264A (en) * | 2011-05-20 | 2011-12-14 | 常州有则科技有限公司 | Titanium/strontium covered nanocrystalline titanium dioxide film for dye-sensitized solar cell and preparation method thereof |
CN102280264B (en) * | 2011-05-20 | 2012-12-19 | 常州有则科技有限公司 | Titanium/strontium covered nanocrystalline titanium dioxide film for dye-sensitized solar cell and preparation method thereof |
CN102983206A (en) * | 2011-09-05 | 2013-03-20 | 北京化工大学 | A method for improving photoelectric conversion performance of a CuInS2 film |
CN102983206B (en) * | 2011-09-05 | 2015-05-13 | 北京化工大学 | A method for improving photoelectric conversion performance of a CuInS2 film |
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CN105374939B (en) * | 2014-08-20 | 2017-10-03 | 清华大学 | A kind of Ca-Ti ore type solar cell and preparation method thereof |
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CN115312665A (en) * | 2022-07-28 | 2022-11-08 | 兰州大学 | Solar cell and preparation method thereof |
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