CN101697320B - Dye-sensitized solar cell photoanode and preparation method thereof - Google Patents

Dye-sensitized solar cell photoanode and preparation method thereof Download PDF

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CN101697320B
CN101697320B CN 200910218663 CN200910218663A CN101697320B CN 101697320 B CN101697320 B CN 101697320B CN 200910218663 CN200910218663 CN 200910218663 CN 200910218663 A CN200910218663 A CN 200910218663A CN 101697320 B CN101697320 B CN 101697320B
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dye
solar cell
sensitized solar
nano
dyestuff
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CN101697320A (en
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李德娜
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Irico Group Corp
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Irico Group Corp
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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

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Abstract

The invention relates to a dye-sensitized solar cell photoanode and a preparation method thereof. The dye-sensitized solar cell photoanode comprises a titanium dioxide nano-porous film and dye monomolecular layers which are deposited on transparent conductive glass; a nano-silicon dioxide barrier layer is deposited on the dye monomolecular layers, and a second layer of dye monomolecular layer is absorbed on the nano-silicon dioxide barrier layer to form the dye-sensitized solar cell photoanode. Because a barrier layer is formed between a dye-sensitized nanocrystalline porous film and an electrolyte, the reverse composite of electrons in the film to the electrolyte is restrained effectively so as to enable a reaction to undergo towards a direction which is favorable for electron transfer, and the adsorbed amount of the dye is increased by sensitizing on a nano-silicon dioxide surface again so as to improve the photoelectric conversion performance of an integral dye-sensitized solar cell. The method for preparing dye-sensitized solar cell photoanode has mild reaction condition, simple operation, safety and reliability.

Description

A kind of dye-sensitized solar cell anode and preparation method thereof
Technical field:
The present invention relates to technical field of solar batteries, especially relate to a kind of dye-sensitized solar cell anode and preparation method thereof.
Background technology:
Along with global energy crisis is serious day by day, the urgent hope of people can be found a kind of clean energy resource of sustainable development.Solar energy receives the concern of countries in the world day by day as a kind of inexhaustible natural energy source.DSSC is compared with the traditional silicon solar cell, and is with low cost, makes simply, becomes the focus of various countries' scholar's research.
The dye-sensitized nano film solar battery battery mainly is made of successively following several parts: transparent conducting glass, nano-TiO 2Porous membrane, dye sensitization layer, electrolyte and to electrode.The operation principle of dye-sensitized solar cells is: the dye molecule of dye sensitization layer absorbs behind the sunlight from the ground state transition to excitation state; The electronics of excitation state dyestuff is injected into rapidly in the conduction band of Nano semiconductor; Diffuse to conductive substrates subsequently, be transferred to electrode through external loop; The dyestuff that is in oxidation state is reduced the electrolyte reducing/regenerating of attitude; The electrolyte of oxidation state is reduced in that electrode is accepted electronics, thereby has finished a cyclic process of electron transport.
In these processes, be accompanied by two back of the body reactions: the recombination reaction that is injected into electron acceptor in electronics in the semiconductor conduction band and oxidation state dyestuff or the electrolyte.Wherein to be caught by the oxidizing component in the electrolyte be the main path of electron loss in the DSSC to conduction band electron.
Summary of the invention:
In order to reduce the electron recombination on TiO2/ dyestuff/electrolyte interface, further improve the photoelectric properties of DSSC, the object of the present invention is to provide a kind of dye-sensitized solar cell anode.
Another object of the present invention provides a kind of preparation method of dye-sensitized solar cell anode.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of dye-sensitized solar cell anode, comprise the nano titania porous membrane and the dyestuff monolayer that are deposited on the transparent conducting glass, depositing nano silicon dioxide barrier layer on the described dyestuff monolayer, absorption second layer dyestuff monolayer constitutes dye-sensitized solar cell anode on the nano silicon barrier layer.
A kind of preparation method of dye-sensitized solar cell anode comprises the steps:
(1) be 10～50nm with particle size, thickness is that the nano titania porous membrane of 10～50 μ m puts into 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, with drying after the absolute ethyl alcohol flushing.
(2) nano-porous film after the above-mentioned dye sensitization being put into volume ratio is 1: 10～1: 50 the tetraethoxysilane and the mixed solution of cyclohexane, press 1%～5% of mixed liquor volume and add surfactant, mixing the back soaked 20～60 minutes, press 40%～70% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 1～12 hour, reactive deposition one deck nanometer titanium dioxide silicon layer;
(3) above-mentioned steps is modified the resulting nano-porous film in back 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, and, promptly formed dye-sensitized solar cell anode with drying after the absolute ethyl alcohol flushing.
Described surfactant is non-ionic surface active agent TritonX-100.
Described dyestuff is that cis two (thiocyanate radical)-two (4,4-dicarboxylic acids-2,2-bipyridine) is closed ruthenium (N3) and derivative N719 dyestuff thereof.
With respect to prior art, beneficial effect of the present invention is: form the barrier layer between the nanocrystalline porous film of dye sensitization and electrolyte, effectively suppressed in the film electronics to electrolytical oppositely compound, reaction is carried out to the direction that helps electron transfer, and by sensitization once more at nano-silica surface, increase the dyestuff adsorbance, thereby improved the photoelectricity conversion performance of whole DSSC.The method reaction condition gentleness, simple to operate, safe and reliable for preparing dye-sensitized solar cell anode among the present invention.
Description of drawings:
Fig. 1 is the structure chart of dye-sensitized solar cell anode of the present invention and cell apparatus.
Among the figure: 1, transparent conducting glass; 2, nano-TiO 2Porous membrane; 3, dyestuff monolayer; 4, nanometer SiO 2The barrier layer; 5, second layer dyestuff monolayer; 6, electrolyte (iodine/lithium iodide); 7, to electrode.
Embodiment:
As shown in Figure 1, a kind of dye-sensitized solar cell anode, comprise the nano titanium dioxide porous film 2 and the dyestuff monolayer 3 that are deposited on the transparent conducting glass 1, depositing nano silicon dioxide barrier layer 4 on the described dyestuff monolayer 3, absorption second layer dyestuff monolayer 5 constitutes dye-sensitized solar cell anode on the nano silicon barrier layer 4.Adopt iodine/lithium iodide electrolyte 6, the electro-conductive glass of platinum plating is assembled into battery as to electrode 7.
The preparation method of dye-sensitized solar cell anode comprises the steps:
(1) be 10～50nm with particle size, thickness is that the nano titania porous membrane of 10～50 μ m puts into 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, with drying after the absolute ethyl alcohol flushing.
(2) nano-porous film after the above-mentioned dye sensitization being put into volume ratio is 1: 10～1: 50 the tetraethoxysilane and the mixed solution of cyclohexane, press 1%～5% of mixed liquor volume and add surfactant, mixing the back soaked 20～60 minutes, press 40%～70% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 1～12 hour, reactive deposition one deck nanometer titanium dioxide silicon layer;
(3) above-mentioned steps is modified the resulting nano-porous film in back 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, and, promptly formed dye-sensitized solar cell anode with drying after the absolute ethyl alcohol flushing.
Described surfactant is non-ionic surface active agent Triton X-100.
Described dyestuff is that cis two (thiocyanate radical)-two (4,4-dicarboxylic acids-2,2-bipyridine) is closed ruthenium (N3) and derivative N719 dyestuff thereof.
Below by embodiment the preparation method of dye-sensitized solar cell anode is described further:
Embodiment one
With particle size is 10nm, and thickness is the TiO of 10 μ m 2Porous membrane is 3.5 * 10 -3Soak after 12 hours in the N3 ethanolic solution of mol/L, with drying behind the absolute ethanol washing, putting into volume ratio again is 1: 50 the tetraethoxysilane and the mixed solution of cyclohexane, press 5% of mixed liquor volume and add surfactant TritonX-100, mix the back and soaked 20 minutes, press 70% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 1 hour, then with acetone washing, drying.With the nano-porous film after modifying 3.5 * 10 -3Soak after 12 hours in the N3 ethanolic solution of mol/L, taking-up is dried, and promptly forms dye-sensitized solar cell anode, adopts iodine/lithium iodide electrolyte, and the electro-conductive glass of platinum plating is assembled into battery as to electrode.
Embodiment two
With particle size is 20nm, and thickness is 50 μ m TiO 2Porous membrane is 3.5 * 10 -5Soak after 1 hour in the N3 ethanolic solution of mol/L, taking-up is dried, putting into volume ratio again is 1: 10 the tetraethoxysilane and the mixed solution of cyclohexane, press 1% of mixed liquor volume and add surfactant TritonX-100, mix the back and soaked 60 minutes, press 40% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 6 hours, then with acetone washing, drying.With the nano-porous film after modifying 3.5 * 10 -5Soak after 1 hour in the N3 ethanolic solution of mol/L, taking-up is dried, and promptly forms dye-sensitized solar cell anode, adopts iodine/lithium iodide electrolyte, and the electro-conductive glass of platinum plating is assembled into battery as to electrode.
Embodiment three
With particle size is 50nm, and thickness is the TiO of 30 μ m 2Porous membrane is 3.5 * 10 -4Soak after 24 hours in the organic solution of the dyestuff of mol/L, taking-up is dried, putting into volume ratio again is 1: 30 the tetraethoxysilane and the mixed solution of cyclohexane, press 2.5% of mixed liquor volume and add surfactant TritonX-100, mix the back and soaked 30 minutes, press 50% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 12 hours, then with acetone washing, drying.With the porous membrane of modified 3.5 * 10 -4Soak after 24 hours in the organic solution of the dyestuff of mol/L, taking-up is dried, and promptly forms dye-sensitized solar cell anode, adopts iodine/lithium iodide electrolyte, and the electro-conductive glass of platinum plating is assembled into battery as to electrode.

Claims (4)

1. dye-sensitized solar cell anode, comprise the nano titania porous membrane and the dyestuff monolayer that are deposited on the transparent conducting glass, it is characterized in that, depositing nano silicon dioxide barrier layer on the described dyestuff monolayer, absorption second layer dyestuff monolayer constitutes dye-sensitized solar cell anode on the nano silicon barrier layer.
2. the preparation method of the described dye-sensitized solar cell anode of claim 1 comprises the steps:
(1) be 10～50nm with particle size, thickness is that the nano titania porous membrane of 10～50 μ m puts into 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, with drying after the absolute ethyl alcohol flushing;
(2) nano-porous film after the above-mentioned dye sensitization being put into volume ratio is 1: 10～1: 50 the tetraethoxysilane and the mixed solution of cyclohexane, press 1%～5% of mixed liquor volume and add surfactant, mixing the back soaked 20～60 minutes, press 40%～70% of tetraethoxysilane volume and add ammoniacal liquor, soaking at room temperature 1～12 hour, reactive deposition one deck nanometer titanium dioxide silicon layer;
(3) above-mentioned steps is modified the resulting nano-porous film in back 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, and, promptly formed dye-sensitized solar cell anode with drying after the absolute ethyl alcohol flushing.
3. the preparation method of dye-sensitized solar cell anode according to claim 2, it is characterized in that: described surfactant is non-ionic surface active agent TritonX-100.
4. the preparation method of dye-sensitized solar cell anode according to claim 2, it is characterized in that: described dyestuff is that cis two (thiocyanate radical)-two (4,4-dicarboxylic acids-2,2-bipyridine) is closed ruthenium N3 or derivatives thereof N719 dyestuff.
CN 200910218663 2009-10-29 2009-10-29 Dye-sensitized solar cell photoanode and preparation method thereof Expired - Fee Related CN101697320B (en)

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CN101937777A (en) * 2010-07-20 2011-01-05 东华大学 Method for manufacturing dye sensitized solar cell
CN102074374B (en) * 2011-02-14 2012-05-23 合肥工业大学 Doping dye sensitized solar cell photo anode, preparation method and application thereof
CN102354606B (en) * 2011-09-24 2013-05-29 东莞电子科技大学电子信息工程研究院 Preparation method of photoanode of dye-sensitized solar cell
WO2013078110A1 (en) * 2011-11-21 2013-05-30 President And Fellows Of Harvard College Self-aligned deposition of silica layers for dye-sensitized solar cells
CN106876145A (en) * 2017-03-24 2017-06-20 湖北大学 A kind of solar cell TiO2/SiO2Core shell structure light anode and preparation method thereof
CN113797970B (en) * 2020-06-01 2023-08-04 中国科学院理化技术研究所 Polypyridine iron complex photocatalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1411077A (en) * 2001-09-26 2003-04-16 北京科技大学 Nano titanium dioxide film and its manufacturing method
CN101071829A (en) * 2007-06-04 2007-11-14 西安交通大学 Method for manufacturing dye sensitized nano crystal solar cell photo-anode membrane
CN101097993A (en) * 2007-06-26 2008-01-02 武汉大学 Process for producing modified polymer electrolyte dye sensitization nanocrystalline solar battery
CN101354968A (en) * 2008-09-16 2009-01-28 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1411077A (en) * 2001-09-26 2003-04-16 北京科技大学 Nano titanium dioxide film and its manufacturing method
CN101071829A (en) * 2007-06-04 2007-11-14 西安交通大学 Method for manufacturing dye sensitized nano crystal solar cell photo-anode membrane
CN101097993A (en) * 2007-06-26 2008-01-02 武汉大学 Process for producing modified polymer electrolyte dye sensitization nanocrystalline solar battery
CN101354968A (en) * 2008-09-16 2009-01-28 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof

Non-Patent Citations (1)

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JP特开2005-79068A 2005.03.24

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