CN100470851C - Post-decoration method for dye sensitization light anode of dye sensitization solar battery - Google Patents
Post-decoration method for dye sensitization light anode of dye sensitization solar battery Download PDFInfo
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- CN100470851C CN100470851C CNB200710119311XA CN200710119311A CN100470851C CN 100470851 C CN100470851 C CN 100470851C CN B200710119311X A CNB200710119311X A CN B200710119311XA CN 200710119311 A CN200710119311 A CN 200710119311A CN 100470851 C CN100470851 C CN 100470851C
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 206010070834 Sensitisation Diseases 0.000 title claims description 25
- 230000008313 sensitization Effects 0.000 title claims description 25
- 238000005034 decoration Methods 0.000 title claims description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 51
- 239000011521 glass Substances 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000002736 metal compounds Chemical group 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000000295 complement effect Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000011010 flushing procedure Methods 0.000 description 14
- 229910010413 TiO 2 Inorganic materials 0.000 description 11
- 238000007747 plating Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002508 compound effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007654 immersion 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
A later-modified method for dye-sensitized photo anode in a dye-sensitized solar cell belongs to the field of dye-sensitized solar cell, which is characterized in that after complement absorbing dye of a prepared nanometer porous TiO2 photo anode, the dye-sensitized photo anode is modified with metal compound layer, and the later-modified method of dye-sensitized photo anode has two advantages: on one hand, preventing agglomeration of dye through exchanging of in-situ proton in order to reduce backward composition of electrodes injected through TiO2 guiding belt and an oxidation-reduction pair in electrolyte and improve photoelectric conversion efficiency of solar cell; on the other hand, separating TiO2 and electrolyte in space to restrain solvent process of dye desorbing from surface of TiO2 and dissolving into electrolyte and preventing electrolyte from being degraded by TiO2 with a good photo-catalysis performance in order to improve stability of solar cell, and after being modified by metal compound layer, the dye-sensitized solar cell improves the photoelectric conversion efficiency by 20 percent and the stability of unsealed battery largely surpasses battery without later-modified layer.
Description
Technical field:
The present invention designs DSSC material field, refers more particularly to the post-decoration method of metallic compound to the nanoporous TiO2 film of dye sensitization
Background technology:
At present in the world 80% energy sources in being the fossil fuel of representative with oil, coal.Along with the rapid increase of world population and the high speed development of human society, human growth and consumption to energy demand is also more and more faster.But as non-renewable energy resources, fossil energy can't satisfy human long-term demand.The demand of the environment amenable renewable energy technologies of people is more and more urgent, and solar cell has attracted people's sight with its exclusive advantage, is considered to the most promising utilization of new energy resources mode.
The stock number of solar energy is very huge, and is subjected to the restriction of geographical conditions hardly, to environment also not influence.The energy that the sun offers the earth is very huge, and can reach 3 * 1024 joules every year, is equivalent to 10000 times of global annual energy demand at present.Solar cell does not have moving component, and the stability of its operation is very high, to not influence of environment.Solar cell directly produces electric energy, and utilization, transmission and distribution are all very convenient, the energy efficiency height, and application is very extensive, from the family life to the industrial production, almost without any restriction, is a kind of very perfect energy sources application form therefore.
The most attracting characteristics of DSSC are cheap cost and simple preparation technologies.M.
The dye sensitization nano-film solar cell sample of professor leader's research group preparation in 1991, under AM1.5 simulated solar irradiation illuminate condition, photoelectric conversion efficiency has reached 7.1%, and monochromatic photoelectric conversion efficiency (IPCE) is greater than 80%.Through research in recent years, the photoelectric conversion efficiency of DSSC surpasses 10%, and has obtained certain progress aspect commercialization.
Present goal in research mainly is further to improve the photoelectric conversion efficiency and the stability of DSSC.Electronics will be through 7 transmittance processs in the DSSC: (1) dyestuff excites; (2) electronics injects TiO2; (3) electronics transmits in TiO2; (4) electronics is reducing I3-to electrode; (5) reducing dyes regeneration; (6) electronics and oxidation state dyestuff are compound; (7) I3-is compound in electronics and the electrolyte.Wherein 7 is main recombination processes.Studies show that in a large number the principal element TiO2 of restriction solar cell photoelectric conversion efficiency and the electron back on dyestuff and the electrolyte interface are to compound.The stability aspect, the volatility of solvent and infiltrative problem are inevitable in the electrolyte, and simultaneously, the existence of electrolyte is corroding electrode easily also, causes the dyestuff desorption, and battery performance descends.Therefore, issue for battery life is the problem that the practicability of DSSC must solve.
The light anode is to the absorption of light in the DSSC, the injection of electronics, and the reverse compound grade of electronics all concentrates on TiO
2On/dyestuff/electrolyte interface, a lot of research work are at TiO
2/ dyestuff modifying interface plays and stops compound effect.If can on dyestuff/electrolyte interface, add the barrier layer, also can play prevention TiO
2In inject electronics and electrolytical compound effect, can suppress in the electrolyte solvent simultaneously to TiO
2Washing away of the dyestuff of last absorption, the efficient and the stability of raising battery.
Summary of the invention:
The objective of the invention is to method, improve the photoelectric conversion efficiency of battery, improve the stability of battery by back modification on the light anode of dye sensitization.
Dye-sensitized solar cell anode of the present invention is the broad stopband nano-porous film, and absorbing dye is afterwards modified and gone up metallic compound then, adds electrolyte assembled battery at last.
The post-decoration method of dye sensitization light anode is characterized in that in the DSSC of the present invention, may further comprise the steps:
1.) preparation dye sensitization light anode
With colloidal tio 2 knifing in the transparent conducting glass substrate, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of following sintering 30min; In the dye solution of 5mmol/L, soak 30min-24h then, obtain dye sensitization light anode;
2) back is modified
Above-mentioned dye sensitization light anode is soaked 1s-12h in the precursor solution of the metallic compound of 0.005-1mol/L, takes out drying, in air, placed 1 hour, it is separated in water in air, generate corresponding metal oxide,
3) assembled battery
To modify to handle on the dye sensitization light anode that obtains through later and add electrolyte and, be assembled into battery electrode.
Described dyestuff is suitable-two (thiocyanate radical)-two (4,4 '-dicarboxylic acids-2,2 '-bipyridine) closes ruthenium (being the N3 dyestuff) or suitable-two (thiocyanate radical)-two (4,4 '-dicarboxylic acid radical TBuA-2,2 '-bipyridine) close ruthenium (being the N719 dyestuff) or three (thiocyanate radicals)-(4,4 ', 4 "-three carboxyls-2; 2 ': 6 ', 2 "-terpyridyl) close the bipyridine complex dye of ruthenium (promptly black dyestuff) or metal Ru.
Wide bandgap semiconductor film in the said method is that preparation is suprabasil at transparent conducting glass, and transparent conducting glass can be the tin ash glass ITO of indium doping or the tin ash glass FTO that fluorine mixes.
Metal ion in the said method is selected from Al
3+, Ga
3+, Ti
4+, Zr
4+, Nb
5+Ion, metallic compound can be with oxide, sulfide, carbonate, sulfate, phosphate, phosphite, hypophosphites, the metaphosphate form exists.Described metallic compound precursor solution solvent is water or isopropyl alcohol organic solvent.
Compare with existing method, after modifying behind the metallic compound, add decorative layer in the middle of dyestuff/electrolyte, reduced the oppositely compound of battery, improved the open circuit voltage and the short circuit current of battery, the photoelectric conversion efficiency of battery improves greatly, and stability also significantly strengthens.
Description of drawings:
Fig. 1: IR spectrum shows Al
2O
3The back is modified protonated to the original position of N3
Be followed successively by (a) 30s from a to the d soak time, (b) 2min, (c) 5min, (d) 15min
Fig. 2: Al
2O
3The dark current of battery before and after the back is modified
A is the not back battery of modifying (Comparative Examples), and b is the battery (embodiment one) that the back is modified.
Fig. 3: Al
2O
3The I-V curve of battery before and after the back is modified
Embodiment:
Comparative Examples: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, taking-up is washed with absolute ethyl alcohol, dry, obtain dye sensitization light anode.Adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2The simulated solar rayed under, the open circuit voltage of the battery that records is 0.65V, short circuit current is 6.24mA/cm
2, fill factor, curve factor 63.9%, total photoelectric conversion efficiency 2.60%.
Example one: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Al[OCH of 0.015mol/L (CH
3)
2]
3Soak in/the aqueous isopropanol behind the 30s with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.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 0.70V, short circuit current is 7.72mA/cm
2, fill factor, curve factor 61.3%, total photoelectric conversion efficiency 3.32%.
Example two: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soaked 24 hours then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Ga of 0.5mol/L (H
2PO
2)
3Soak in/the aqueous isopropanol behind the 15min with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.Adopt quasi-solid electrolyte, the electro-conductive glass of platinum plating is assembled into battery as to electrode.At 100mW/cm
2The simulated solar rayed under, the open circuit voltage of the battery that records is 0.68V, short circuit current is 7.24mA/cm
2, fill factor, curve factor 63.9%, total photoelectric conversion efficiency 3.15%.
Example three: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soaked 12 hours then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Ti of 1mol/L (OC
4H
9Soak in the)/butanol solution behind the 2min with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.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 0.713V, short circuit current is 7.18mA/cm
2, fill factor, curve factor 64.9%, total photoelectric conversion efficiency 3.32%.
Example four: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Zr of 0.005mol/L
3(PO
4)
4Soak in the solution behind the 1s with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.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 0.68V, short circuit current is 7.52mA/cm
2, fill factor, curve factor 62.5%, total photoelectric conversion efficiency 3.20%.
Example five: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Nb of 0.015mol/L
2S
5Immersion with drying behind the alcohol flushing, was placed 1 hour in air after 12 hours in the/aqueous isopropanol, obtained dye sensitization light anode.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 0.69V, short circuit current is 7.10mA/cm
2, fill factor, curve factor 64%, total photoelectric conversion efficiency 3.13%.
Example six: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Zr of 0.015mol/L (SO
4)
2Soak in the solution behind the 5min with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.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 0.70V, short circuit current is 7.68mA/cm
2, fill factor, curve factor 62.4%, total photoelectric conversion efficiency 3.35%.
Example seven: with colloidal tio 2 knifing on transparent conducting glass ITO, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of sintering 30min, in the dye solution of 5mmol/L, soak 30min then, take out with the absolute ethyl alcohol flushing, with this TiO
2Perforated membrane is at the Ti of 15mmol/L (HCO
3)
2Soak in the solution behind the 1s with drying behind the alcohol flushing, in air, placed 1 hour, obtain dye sensitization light anode.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 0.69V, short circuit current is 7.62mA/cm
2, fill factor, curve factor 63.3%, total photoelectric conversion efficiency 3.33%.
After battery in the Comparative Examples was placed one day in air, efficient dropped to 0.36% from 2.60%, and open circuit voltage drops to 0.565V from 0.65V, and short circuit current drops to 1mA/cm from 6.24
2Under the battery kindred circumstances in the example one, efficient drops to 3.20% from 3.32%, and open circuit voltage is reduced to 0.685V from 0.70V, and short circuit current is elevated to 7.88mA/cm from 7.72
2
Placed two days, the battery in the Comparative Examples has only 0.18% efficient, and the battery in the example one still has 1.98% efficient.
Modify the infrared spectrum of the sensitization light anode of different time behind Fig. 1.N3 is the sample of modifying without the back, and a～d is followed successively by the back and modifies that time span is 1,2,5, the sample of 15min.1380cm as seen from the figure, 1600,
-1The carbonyl peak of the carboxylate radical at place increases with modification time lengthening, and the interaction between the metal oxide and N3 dyestuff in the back modification has been described.
Fig. 2 sample battery dark current curve.A modifies without the back, and b is after modifying later.As seen from the figure, through modifying later, the dark current under the same voltage reduces significantly.
The current-voltage curve of the sample battery of modification time after Fig. 3 difference.As seen from the figure, the battery of back modification 30s has provided the highest photoelectricity flow valuve and photovoltage value, battery performance the best.Back modification time lengthening, photoelectric current has decline slightly, and photovoltage has raising slightly.
Claims (5)
1. the post-decoration method of dye sensitization light anode in the DSSC is characterized in that, may further comprise the steps:
1.) preparation dye sensitization light anode
With colloidal tio 2 knifing in the transparent conducting glass substrate, obtain the wide bandgap semiconductor titanium deoxid film of nano-porous structure at 450 ℃ of following sintering 30min; In the dye solution of 5mmol/L, soak 30min-24h then, obtain dye sensitization light anode;
2) back is modified
Above-mentioned dye sensitization light anode is soaked 1s-12h in the precursor solution of the metallic compound of 0.005-1mol/L, takes out drying, in air, placed 1 hour, it is separated in water in air, generate corresponding metal oxide,
3) assembled battery
To modify to handle on the dye sensitization light anode that obtains through later and add electrolyte and, be assembled into battery electrode.
2. post-decoration method as claimed in claim 1, it is characterized in that, described dyestuff is that suitable-two (thiocyanate radical)-two (4,4 '-dicarboxylic acids-2,2 '-bipyridine) close ruthenium or suitable-two (thiocyanate radical)-two (4,4 '-dicarboxylic acid radical TBuA-2,2 '-bipyridine) close ruthenium or three (thiocyanate radical)-(4,4 ', 4 "-three carboxyls-2; 2 ': 6 ', 2 "-terpyridyl) close the bipyridine complex dye of ruthenium or metal Ru.
3. post-decoration method as claimed in claim 1 is characterized in that, described metallic compound precursor solution solvent is water or isopropyl alcohol organic solvent.
4. post-decoration method as claimed in claim 1 is characterized in that, metal ion is selected from Al in the described precursor solution of described metallic compound
3+, Ga
3+, Ti
4+, Zr
4+, Nb
5+Ion.
5, post-decoration method as claimed in claim 1 is characterized in that, described metallic compound is with oxide, sulfide, and carbonate, sulfate, phosphate, phosphite, hypophosphites, the metaphosphate form exists.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710119311XA CN100470851C (en) | 2007-07-20 | 2007-07-20 | Post-decoration method for dye sensitization light anode of dye sensitization solar battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB200710119311XA CN100470851C (en) | 2007-07-20 | 2007-07-20 | Post-decoration method for dye sensitization light anode of dye sensitization solar battery |
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| CN101345140B (en) * | 2008-08-12 | 2011-03-16 | 浙江科技学院 | Preparation method for optical anode of dye sensitization solar battery |
| CN101866753B (en) * | 2009-04-16 | 2012-05-16 | 中国科学院物理研究所 | Photoanode surface treatment method of dye sensitization solar batteries |
| CN101872865B (en) * | 2009-04-24 | 2012-04-25 | 中国科学院化学研究所 | Photo-induced hydroxyl ionized solar battery |
| CN101872866B (en) * | 2009-04-24 | 2012-04-25 | 中国科学院化学研究所 | Photo-induced protonized solar battery |
| CN101773820B (en) * | 2009-12-30 | 2012-11-21 | 长沙学院 | Method for preparing visible light active photocatalyst through dye sensitization |
| CN102254696B (en) * | 2011-04-29 | 2013-01-02 | 苏州大学 | Photoanode decoration material of dye sensitized solar cell |
| CN102558066B (en) * | 2011-12-23 | 2014-04-16 | 苏州大学 | Cyanobiphenyl-functionalized benzimidazole compound, and preparation and application thereof |
| CN104347275A (en) * | 2013-07-30 | 2015-02-11 | 清华大学 | All-solid-state sensitized solar cell and preparation method thereof |
| 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 |
| CN106373784B (en) * | 2015-07-22 | 2019-02-05 | 清华大学 | A kind of Ca-Ti ore type solar battery and preparation method thereof |
| CN115360023A (en) * | 2022-08-29 | 2022-11-18 | 南京大学 | Thermal sensitive titanium dioxide photo-anode and preparation method thereof |
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| 染料敏化纳米太阳能电池. 李斌，邱勇.感光科学与光化学，第18卷第4期. 2000 |
| 染料敏化纳米太阳能电池. 李斌，邱勇.感光科学与光化学，第18卷第4期. 2000 * |
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