WO2013011786A1 - Colorant pour une cellule solaire sensibilisée aux colorants, élément de conversion photoélectrique comprenant ledit colorant et cellule solaire sensibilisée aux colorants - Google Patents

Colorant pour une cellule solaire sensibilisée aux colorants, élément de conversion photoélectrique comprenant ledit colorant et cellule solaire sensibilisée aux colorants Download PDF

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WO2013011786A1
WO2013011786A1 PCT/JP2012/065561 JP2012065561W WO2013011786A1 WO 2013011786 A1 WO2013011786 A1 WO 2013011786A1 JP 2012065561 W JP2012065561 W JP 2012065561W WO 2013011786 A1 WO2013011786 A1 WO 2013011786A1
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dye
sensitized solar
solar cell
tio
electrode
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PCT/JP2012/065561
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English (en)
Japanese (ja)
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伊藤　省吾
高橋　薫
昌幸 齊藤
利幸 重富
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田中貴金属工業株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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

Definitions

  • the present invention relates to a dye for a dye-sensitized solar cell for improving the thermal durability of a dye-sensitized solar cell, a photoelectric conversion element using the dye, and a dye-sensitized solar cell.
  • Dye-sensitized solar cells are characterized by low cost in terms of raw materials and manufacturing, high designability such as colorfulization, and high output under fluorescent lamps.
  • a dye-sensitized solar cell is a solar cell that generates electricity based on a chemical reaction similar to plant photosynthesis, and when irradiated with visible light, the sensitizing dye absorbs light and enters an excited state.
  • the electrons are injected into the conduction band of the titanium oxide semiconductor, the injected electrons move to the counter electrode through an external circuit, and the transferred electrons are carried by the ions in the electrolyte and return to the sensitizing dye. Is repeated to extract electric energy.
  • a K19 dye (Ru (4,4′-dicarboxylic acid-2,2′-bipyridine) (4,4′-bis (p-hexyloxystyryl) -2,2′-bipyridine) (NCS) 2 ) used as a sensitizing dye, as an electrolytic solution, 1 Puropiru 3- methylimidazolium iodide, iodine, employing 3-methoxy propionitrile solution containing guanidine thiocyanate and N- methylbenzimidazole, the porous TiO 2 film
  • the nanocrystalline TiO 2 dye-sensitized solar cell co-grafted with 1-decylphosphonic acid on the surface of the sensitizing dye showed a conversion efficiency of 8% or more after 1000 hours of thermal stress at 80 ° C. Has been reported (see Non-Patent Document 1).
  • Non-Patent Document 2 a current collector wiring type ionic liquid dye-sensitized solar cell manufactured using a multi-layer wiring protective layer having a reinforced wiring protective layer and a moisture-resistant package that prevents moisture from entering is 85 ° C., 85% RH. It has been reported that the durability evaluation items defined in JIS such as 1000 hours can be cleared (see Non-Patent Document 2).
  • the sensitizing dye used in the dye-sensitized solar cell is improved to a ruthenium dye containing a crosslinkable olefin group polymerizable on a porous TiO 2 electrode, and an acetonitrile / tert-butanol mixed solution containing this ruthenium dye is prepared.
  • Heat-gelled polymethacrylate gel electrolyte is used as the electrolyte solution, and this is sealed between the electrodes.
  • DOO-like hot melt by sealant dye-sensitized solar cell sealing the inlet of the electrolyte solution, N3 dye containing no crosslinkable olefinic groups (Ru (4,4' Jikarubokishi 2,2'-bipyridine) 2 (NCS) 2 ) papers have been published that report that the conversion efficiency is improved by 5% or more, the shelf life is prolonged, and the durability is improved (Non-patent Document 3). reference). However, the durability test only reported the deterioration at room temperature.
  • the thermal durability of the conventional dye-sensitized solar cell is limited to 85 ° C., and the thermal durability is still insufficient for commercialization as a solar cell product.
  • the improvement of this was one of the issues to be overcome. Accordingly, in view of such circumstances, the present invention provides a dye for a dye-sensitized solar cell for improving the thermal durability of a dye-sensitized solar cell, a photoelectric conversion element using the dye, and a dye-sensitized solar.
  • An object is to provide a battery.
  • the present inventors synthesized a novel ruthenium complex dye having a long alkyl group having a vinyl group introduced at the terminal as a sensitizing dye, and as an electrolyte, A dye-sensitized solar cell was fabricated by heat treatment at a temperature higher than the conventional range of 100 to 120 ° C using an ionic liquid with high heat durability instead of an organic solvent such as acetonitrile.
  • the present inventors have found that the thermal durability is improved from 85 ° C. to 120 ° C., and have completed the present invention based on such knowledge.
  • the present invention relates to a dye comprising Ru (4,4′-di (9-nonenyl) -2,2′-bipyridine) (4,4′-dicarboxy-2,2′-bipyridine) (NCS) 2 It is a dye for sensitized solar cells.
  • the present invention also provides a photoelectric conversion element comprising a transparent conductive substrate and a porous film formed on the transparent conductive substrate, wherein the porous film adsorbs the dye for dye-sensitized solar cells.
  • a photoelectric conversion element is composed of TiO 2 particles.
  • the present invention is a dye-sensitized solar cell using the photoelectric conversion element.
  • the present invention greatly contributes to the future spread of dye-sensitized solar cells.
  • Is a diagram showing the absorbance of the porous was supported in TiO 2 film porous TiO 2 electrode N719 dye, the horizontal axis represents units wavelength nm, the vertical axis represents the absorbance.
  • Is a diagram showing the absorbance of the porous was supported in TiO 2 film porous TiO 2 electrode Z907 dye, the horizontal axis represents units wavelength nm, the vertical axis represents the absorbance.
  • Is a diagram showing the absorbance of the porous was supported in TiO 2 film porous TiO 2 electrode SG1051 dye, the horizontal axis represents units wavelength nm, the vertical axis represents the absorbance.
  • Is a diagram showing the absorbance of the porous was supported in TiO 2 film porous TiO 2 electrode SG1051 dye heated at 125 ° C., the horizontal axis represents units wavelength nm, the vertical axis represents the absorbance.
  • Is a diagram showing the absorbance of the porous was supported in TiO 2 film porous TiO 2 electrode SG1051 dye was heated at 250 ° C., the horizontal axis represents units wavelength nm, the vertical axis represents the absorbance.
  • the dye for a dye-sensitized solar cell of the present invention is Ru (4,4′-di (9-nonenyl) -2,2′-bipyridine) (4,4′-dicarboxy-2,2′-bipyridine).
  • (NCS) 2 hereinafter abbreviated as “SG1051 dye”
  • the dye for a dye-sensitized solar cell is surrounded by an electrolyte solution, it is easily detached from the surface of the TiO 2 electrode.
  • the dye of the present invention is strongly bonded to the surface of the porous TiO 2 , It is possible to obtain a dye-sensitized solar cell that generates less dye in the environment and thus has excellent thermal durability.
  • the dye of the present invention is combined with an electrolyte solution composed of a predetermined ionic liquid described later, and further, the dye is adsorbed on the electrode and then heated in a predetermined temperature range, thereby heating the dye-sensitized solar cell. Durability can be further improved.
  • the method for producing the dye for a dye-sensitized solar cell of the present invention comprises 4,4′-di (9-nonenyl) -2,2′-bipyridine, using dichloro (p-cymene) ruthenium (II) dimer as a starting material, It can be prepared by sequentially reacting with 4,4′-dicarboxy-2,2′-bipyridine and sodium thiocyanate.
  • dye is not limited to this.
  • 4,4′-di (9-nonenyl) -2,2′-bipyridine can be prepared, for example, as follows. First, a hexane solution of n-butyllithium was added to a tetrahydrofuran solution of diisopropylamine at 0 to 5 ° C. and stirred for 0.5 to 1.0 hour, followed by addition of 4,4′-dimethyl-2,2′-bipyridine in tetrahydrofuran. Add the solution dropwise. After the dropwise addition, the mixture is stirred at -70 to -60 ° C for 3 to 4 hours.
  • 9-iodinated nonene may be prepared by using a known technique for iodination of alcohol.
  • triphenylphosphine imidazole is added to a mixed solution of starting material 9-nonen-1-ol in diethyl ether / acetonitrile. , And iodine to obtain alcohol by iodination.
  • the photoelectric conversion element of the present invention uses the above-described dye, and can be produced, for example, by the following method.
  • a transparent conductive substrate having a transparent conductive film formed on an electrode substrate is prepared.
  • the electrode substrate is preferably light transmissive, and examples thereof include plates and films made of glass, ceramics, plastics, and the like.
  • the transparent conductive film a film in which tin oxide is doped with fluorine (FTO film), a film in which a small amount of tin oxide is added to indium oxide (ITO film), a film in which tin oxide is doped with antimony (ATO film), oxidation Tin etc. are mentioned.
  • the transparent conductive substrate is produced by forming a transparent conductive film on one surface, both surfaces, or the entire surface of the electrode substrate by a spray pyrolysis method, a vapor deposition method, a sputtering method, an ion plating method, a hydrolysis method, or the like.
  • a porous film is produced on the transparent conductive film of the transparent conductive substrate.
  • an n-type metal oxide semiconductor film made of titanium oxide or the like is preferable, and a porous TiO 2 film obtained by applying and baking a TiO 2 paste is particularly preferable.
  • the TiO 2 paste is prepared by adding and mixing TiO 2 particles in an aqueous solvent to prepare a dispersion, and adding a thickener, a dispersant, and the like to the dispersion and mixing them uniformly.
  • the TiO 2 paste is applied by a doctor blade method, a squeegee method, a spin coating method, a screen printing method, an electrodeposition method, a spray method, and the like, dried, and then placed in an electric furnace.
  • the porous film is formed on the transparent conductive film by firing at 300 to 700 ° C. for 10 to 60 minutes in the air. This porous film constitutes a photoelectric conversion element together with the transparent conductive substrate and the dye.
  • the firing temperature is less than 300 ° C., sintering of the TiO 2 particles becomes insufficient, so that the adsorption of the dye is hindered and high photoelectric conversion characteristics cannot be obtained, and if it exceeds 700 ° C., the transparent conductive substrate may be defective. is there. Further, if the firing time is less than 10 minutes, the sintering becomes insufficient, and if it exceeds 60 minutes, the grain growth due to firing proceeds so much that the specific surface area may be lowered.
  • the porous film on the transparent conductive film can be not only a single layer but also a multilayer structure of two or more layers.
  • the average particle diameter using the diameter when the projected area is converted into a circle is 5 to 5 as primary particles.
  • a transparent layer composed of 200 nm TiO 2 particles is formed, and a light scattering layer composed of TiO 2 particles having an average particle diameter of 100 to 600 nm is formed thereon.
  • a transparent conductive substrate having a porous film formed on the transparent conductive film is immersed in a dye solution, thereby adsorbing and fixing the dye to the porous film.
  • the dye solution is obtained by mixing the dye of the present invention with hydrocarbons such as hexane, octane, toluene and xylene, aliphatic alcohols such as methanol, ethanol, propanol and normal butanol, nitriles such as acetonitrile and propionitrile, acetone and methyl ethyl ketone.
  • Ketones such as ethyl acetate and butyl acetate, carbonates such as diethyl carbonate and propylene carbonate, carbonates such as dimethyl carbonate and diethyl carbonate, lactones, amides such as dimethylformamide and dimethylacetamide, caprolactam And a single solvent such as sulfones such as dimethyl sulfoxide and sulfolane or a mixed solvent thereof.
  • aliphatic alcohols and nitriles are used.
  • the dye concentration in the dye solution is 0.01 mM or more, preferably 0.1 to 10 mM.
  • the transparent conductive substrate is immersed in the dye solution at 10 to 40 ° C. for about 1 to 24 hours.
  • ultrasonic vibration can be applied to improve the efficiency of dye adsorption to the porous film.
  • the immersion can be performed at room temperature for 5 to 60 minutes.
  • the porous membrane surface adsorbing the dye is washed and then dried.
  • a photoelectric conversion element including a transparent conductive substrate having light transparency and a porous film formed on the transparent conductive substrate, wherein the porous film adsorbs at least the dye of the present invention.
  • a photoelectric conversion element composed of two particles is obtained.
  • the temperature is 120 to 300 ° C., preferably 150 to 300 ° C., for 0.5 to 60 minutes.
  • this heat treatment may be performed as a main seal or end seal treatment in producing a dye-sensitized solar cell.
  • the above heat treatment causes the polymerization between the dyes of the present invention to progress so that the SG1051 dye is not further desorbed, and the dye desorption, which is the main cause of the deterioration of the characteristics of the dye-sensitized solar cell, is reduced.
  • dye of this invention is superposed
  • the photoelectric conversion element of the present invention is strongly bonded to TiO 2 particles by forming a bond between the dye molecules or between the dye and the TiO 2 particle surface by two terminal vinyl functional groups having the appropriate length of the dye of the present invention. Since it is adsorbed, dye desorption that occurs in a high-temperature environment is greatly reduced as compared with conventional dyes, so that heat durability is excellent. Moreover, since the pigment
  • a transparent conductive substrate having a transparent conductive film formed on an electrode substrate is prepared, and a counter electrode is produced by forming a conductive film on the transparent conductive film.
  • the electrode substrate is preferably light transmissive, and examples thereof include plates and films made of glass, ceramics, plastics, and the like.
  • the transparent conductive film a film in which tin oxide is doped with fluorine (FTO film), a film in which a small amount of tin oxide is added to indium oxide (ITO film), a film in which tin oxide is doped with antimony (ATO film), oxidation Tin etc. are mentioned.
  • the transparent conductive substrate is produced by forming a transparent conductive film on one surface, both surfaces, or the entire surface of the electrode substrate by a spray pyrolysis method, a vapor deposition method, a sputtering method, an ion plating method, a hydrolysis method, or the like.
  • Examples of the conductive film formed on the transparent conductive film include a thin film made of platinum, carbon, or the like.
  • the conductive film is formed by a vapor deposition method, a sputtering method, an ion plating method, a hydrolysis method, or the like.
  • the thickness of the conductive film is generally several nm.
  • the photoelectric conversion element and the counter electrode are opposed to each other with a predetermined gap, they are bonded together via a sealing material (main sealing material), and an electrolyte solution is injected between the electrodes to form an electrolyte layer.
  • a sealing material end seal material
  • the end seal material is sealed with a cover material made of glass or the like.
  • the main sealing material include a hot melt material, an ultraviolet curable resin, a thermosetting resin, and a glass frit.
  • sealing is performed by heating at a temperature of 120 to 300 ° C., preferably 150 to 300 ° C.
  • a main seal material made of a hot melt material for a time range of 0.5 to 60 minutes, using a main seal material made of a hot melt material.
  • a main seal material made of a hot melt material include hot melt gasket made of ionomer resin (Surlyn 1702, trade name, thickness 25 ⁇ m, manufactured by DuPont), hot melt gasket made of polyethylene resin (Bynel, trade name) And a thickness of 25 ⁇ m, manufactured by DuPont).
  • the electrolytic solution sealed between the photoelectric conversion element and the counter electrode includes a supporting electrolyte made of a cation such as lithium ion or an anion such as iodine ion, and a redox pair such as iodine-iodine compound or bromine-bromine compound. It is prepared by mixing with a solvent.
  • the solvent examples include water, alcohols, nitriles, ethers, esters, ketones, lactones, heterocyclic compounds, amides, nitromethane, halogenated hydrocarbons, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, Examples thereof include single solvents or mixed solvents such as 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, and hydrocarbons.
  • An ionic liquid such as a salt is preferable, and an imidazolium borate is more preferable.
  • 1-ethyl-3-methylimidazolium tetracyanoborate is preferable from the viewpoint of improving thermal stability.
  • An ionic liquid is a salt composed only of positive and negative ions, and since it has a low melting point, it is liquid at room temperature, is not volatile, and is effective in preventing deterioration of the characteristics of a dye-sensitized solar cell over time.
  • Particularly suitable electrolyte compositions include 0.2-2M 1-ethyl-3-methylimidazolium iodide, 0.2-2M 1,3-dimethylimidazolium iodide, 0.1-1M guanidine.
  • Examples are 1-ethyl-3-methylimidazolium tetracyanoborate solution containing thiocyanate, 0.1-1M N-butylbenzimidazole, 0.05-0.5M iodine.
  • This electrolytic solution is excellent in thermal stability and hardly causes electrode alteration.
  • a through hole injection port
  • the electrolytic solution is injected through the through hole, and after the injection, the through hole is sealed with a sealing material (end seal material).
  • a method of reducing the pressure in a state of being immersed in the electrolytic solution and then releasing the pressure to normal pressure is exemplified, and thus, the space between the photoelectric conversion element and the counter electrode can be easily filled with the electrolytic solution.
  • Examples of the material of the sealing material (end seal material) that seals the through hole (injection port) after injecting the electrolytic solution include a hot melt material, an ultraviolet curable resin, a thermosetting resin, and a glass frit. .
  • the dye of the present invention has two terminal vinyl functional groups having an appropriate length, thereby forming a bond between the dye molecules or between the dye and the TiO 2 particle surface.
  • suction to a porous membrane is used, it can produce comparatively easily.
  • desorbs by continuous use of a photoelectric conversion element a complicated process is not required to return to the original state.
  • the dye-sensitized solar cell of the present invention is not limited to the sandwich-type structure described above, but can be integrated into a plurality of structures to form an arbitrary structure such as a W-type integrated structure, a Z-type integrated structure, or a monolithic integrated structure. By accumulating a plurality, the output can be increased.
  • FTO glass substrate which is conductive glass substrate with FTO film Tec7 (trade name, manufactured by Nippon Sheet Glass Co., Ltd.) is cut into a 25 mm ⁇ 75 mm square, washed with 50 mM hydrochloric acid for 5 minutes and with acetone for 5 minutes using the ultrasonic bath, and again with hydrochloric acid and acetone for 15 minutes each. Washed one by one. After the washing was completed, it was carefully washed with water and ethanol, dried, and treated with the UV-O 3 system for 18 minutes. The FTO glass substrate after the UV-O 3 treatment was placed in a 40 mM TiCl 4 aqueous solution, held at 70 ° C.
  • a TiO 2 paste (PST-400C, trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.) having a particle size of 400 nm is applied on the transparent layer by screen printing, dried and fired, and a film thickness of 4-5 ⁇ m A light scattering layer was formed.
  • the TiO 2 electrode thus produced was put in an electric furnace, dried and fired at 325 ° C. for 5 minutes, 375 ° C. for 5 minutes, 450 ° C. for 15 minutes, and finally at 500 ° C. for 15 minutes, and FTO glass A porous TiO 2 film consisting of two layers was formed on the substrate.
  • the TiO 2 electrodes were placed in a TiCl 4 aqueous solution of 40 mM, after maintaining at 70 ° C. 30 minutes, rinse with water and ethanol removed, 50 mM until use It was immersed in hydrochloric acid and stored.
  • the TiO 2 electrode taken out from hydrochloric acid was rinsed with ethanol and then baked at 500 ° C. for 30 minutes using a heat gun. After air cooling to 80 ° C., the baked TiO 2 electrode was immersed in an acetonitrile / valeronitrile (1: 1) mixed solution containing 0.3 mM SG1051 dye for 1 hour at room temperature to adsorb the dye.
  • FTO glass (LOF Tec7, trade name, manufactured by Nippon Sheet Glass Co., Ltd., thickness mm) was cut into a size of 12 mm ⁇ 12 mm square. A through hole having a diameter of 1 mm was formed at a position 8 mm ⁇ 8 mm from one corner of the FTO glass with a hand drill (U-hoby, trade name, Urawa Kogyo Co., Ltd.). In order to remove dust such as glass pieces from the FTO glass having the through holes, the glass was washed with water for 10 minutes. Next, it was washed with 50 mM hydrochloric acid for 5 minutes, rinsed with acetone, and then washed with acetone for 5 minutes.
  • hand drill U-hoby, trade name, Urawa Kogyo Co., Ltd.
  • the width of the sealing material was 1 mm, and the opening provided was 2 mm larger than the TiO 2 electrode.
  • a through hole was opened in the sealing material using a needle. Then, one drop of the electrolytic solution was dropped in this through hole, placed in a small vacuum chamber, and the electrolytic solution was put into the cell by reverse vacuum transfer. Finally, the through hole was sealed with a hot melt ionomer at a temperature of 250 ° C. for 1 to 3 minutes, and further sealed with a cover glass to produce a sandwich type dye-sensitized solar cell.
  • a hot melt ionomer at a temperature of 250 ° C. for 1 to 3 minutes
  • a cover glass to produce a sandwich type dye-sensitized solar cell.
  • the position of the solder was 1 mm outside from the end of the gasket, that is, 4 mm outside from the end of the TiO 2 layer.
  • a black plastic type mask was attached to the assembled cell.
  • a cell antireflection film (Arctop, trade name, manufactured by Asahi Glass Co., Ltd.) was applied to the filter.
  • the electrolyte includes 0.75M 1-ethyl-3-methylimidazolium iodide, 0.75M 1,3-dimethylimidazolium iodide, 0.2M guanidine thiocyanate, 0.2M N-butylbenzoate.
  • Thermal durability test The above dye-sensitized solar cell prepared using SG1051 dye is placed in a constant temperature oven (AS ONE) at 120 ° C., and the photoelectric characteristics (open circuit voltage (V), short-circuit current density (V), short-circuit current density ( The thermal durability of the dye-sensitized solar cell was evaluated by examining the time course of short circuit current density (mA / cm 2 ), fill factor, and conversion efficiency (%). The conversion efficiency (%) was determined by (open circuit voltage ⁇ short circuit current ⁇ fill factor) / energy of incident light.
  • FIG. 1 is a diagram showing a change in the open circuit voltage of the dye-sensitized solar cell with respect to the elapsed time
  • FIG. 2 is a diagram showing a change in the short-circuit current density of the dye-sensitized solar cell with respect to the elapsed time
  • FIG. 4 is a figure which shows the change with respect to the elapsed time of the conversion efficiency of a dye-sensitized solar cell.
  • the photoelectric characteristics of the dye-sensitized solar cell are obtained by changing the load between the electrodes of the dye-sensitized solar cell using an AM 1.5 solar simulator (manufactured by Yamashita Denso Co., Ltd.) equipped with a 450 W xenon lamp. The current value and the voltage between the electrodes were plotted on a current-voltage curve obtained by plotting.
  • a reference Si photodiode equipped with an IR cut-off filter manufactured by Spectrometer Co., Ltd.
  • the output of simulated light was 100 mW / cm 2 .
  • the current-voltage curve was created by applying an external bias to the dye-sensitized solar cell and measuring the generated photocurrent with a digital source meter (ADMT).
  • the voltage step was set to 10 mV.
  • the photocurrent delay time was set to 500 ms.
  • the Z907 dye is detached from the porous TiO 2 film, but the SG1051 dye is polymerized with each other, so that even if some of the dye is detached from the porous TiO 2 film, Therefore, it is considered that they were not completely detached from the porous TiO 2 film.
  • the porous TiO 2 electrode as will be described later, the absorbance before and after the treatment with the aqueous sodium hydroxide solution (or the aqueous sodium hydroxide solution and acetonitrile) is measured, and the strength of the adsorptive power of each dye and the porous TiO 2 electrode is measured. Were compared.
  • the absorbance of the TiO 2 electrode was measured by irradiating monochromatic light having a wavelength (380 to 800 nm) with an absorbance meter and measuring the reflection of the monochromatic light.
  • the absorbance of the TiO 2 electrode is measured, if the absorbance decreases, it indicates that the dye is desorbed, and the strength of adsorption between the dye and the porous TiO 2 electrode is compared according to the degree of change in absorbance. can do.
  • Sodium hydroxide is an effective reagent for removing the dye from the TiO 2 surface.
  • the absorbance of the TiO 2 electrode washed with acetonitrile and dried was measured.
  • the results are shown in FIG. 7 (the horizontal axis represents wavelength, the unit is nm, and the vertical axis represents absorbance).
  • the absorbance of the TiO 2 electrode washed with water and dried was measured. Immersion in a sodium hydroxide solution was performed for 30 seconds. Further, after the immersion in the sodium hydroxide solution, the absorbance of the TiO 2 electrode washed with acetonitrile and dried was measured. The results are shown in FIG. 8 (the horizontal axis represents wavelength, the unit is nm, and the vertical axis represents absorbance).
  • the absorbance of the TiO 2 electrode washed with water and dried was measured. Immersion in a sodium hydroxide solution was performed for 30 seconds. Further, after the immersion in the sodium hydroxide solution, the absorbance of the TiO 2 electrode washed with acetonitrile and dried was measured. The results are shown in FIG. 9 (the horizontal axis represents wavelength, the unit is nm, and the vertical axis represents absorbance).
  • the SG1051 dye of the present invention is strongly adsorbed to the porous TiO 2 electrode, there is little dye desorption that is the main cause of the deterioration of the characteristics of the dye-sensitized solar cell, and therefore the heat of the dye-sensitized solar cell It was confirmed that it is very useful as a pigment for improving durability.

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Abstract

L'invention vise à fournir un colorant pour des cellules solaires sensibiliséeS aux colorants lequel est utile en tant que colorant sensibilisateur pour améliorer la durabilité thermique, un élément de conversion photoélectrique comprenant le colorant et une cellule solaire sensibilisée aux colorants. A cet effet, selon l'invention, Ru(4,4'-di(9-nonényl)-2,2'-bipyridine)(4,4'- dicarboxy-2,2'-bipyridine)(NCS)2 est utilisé en tant que colorant sensibilisateur.
PCT/JP2012/065561 2011-07-15 2012-06-19 Colorant pour une cellule solaire sensibilisée aux colorants, élément de conversion photoélectrique comprenant ledit colorant et cellule solaire sensibilisée aux colorants WO2013011786A1 (fr)

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