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WO2011087099A1 - Cellule photochimique comprenant des particules semi-conductrices fines sensibilisées par un colorant à complexe de ruthénium binucléaire et solution d'électrolyse contenant un composé de sel d'ammonium ou un composé de sel de phosphonium - Google Patents

Cellule photochimique comprenant des particules semi-conductrices fines sensibilisées par un colorant à complexe de ruthénium binucléaire et solution d'électrolyse contenant un composé de sel d'ammonium ou un composé de sel de phosphonium Download PDF

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Publication number
WO2011087099A1
WO2011087099A1 PCT/JP2011/050572 JP2011050572W WO2011087099A1 WO 2011087099 A1 WO2011087099 A1 WO 2011087099A1 JP 2011050572 W JP2011050572 W JP 2011050572W WO 2011087099 A1 WO2011087099 A1 WO 2011087099A1
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Prior art keywords
salt compound
ion
nitrogen
bipyridine
electrolyte solution
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English (en)
Japanese (ja)
Inventor
青木　崇
貴文 岩佐
剛久 角田
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Ube Corp
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Ube Industries Ltd
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    • 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
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • 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
    • 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
    • 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
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • 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
    • 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 is a photochemistry comprising a photoelectric conversion element comprising semiconductor fine particles sensitized by a dinuclear ruthenium complex dye having a high extinction coefficient and excellent in electron transfer, and an electrolyte solution containing an ammonium salt compound or a phosphonium salt compound. It relates to batteries.
  • Solar cells are highly expected as a clean renewable energy source.
  • all of the batteries must be overcome, such as high manufacturing costs, difficulty in securing raw materials, recycling problems, and difficulty in increasing the area. Have problems.
  • solar cells using organic materials have been proposed with the aim of increasing the area and reducing the price, but all have a conversion efficiency of about 1%, which is far from practical use.
  • This solar cell can be used as an inexpensive photoelectric conversion element because it is not necessary to purify an inexpensive material with high purity, and further, the absorption of the dye used is broad, and a wide wavelength range of visible light It is possible to convert sunlight into electricity. However, further improvement in conversion efficiency is necessary for practical use, and development of a dye having a higher extinction coefficient and absorbing light up to a higher wavelength region is desired.
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-261536 by the present applicant discloses a dipyridyl ligand-containing metal mononuclear complex which is a metal complex dye useful as a photoelectric conversion element.
  • non-patent document 2 discloses polynuclear ⁇ -diketonate complex dyes.
  • Patent Document 3 describes a plurality of metals and a plurality of coordinations as a novel binuclear complex having an excellent photoelectric conversion function for extracting electrons by receiving energy of active light such as light.
  • a binuclear complex having a coordination structure in which a bridging ligand (BL) having a conjugated group and a metal coordinated to a plurality of metals has a heteroconjugated ring and a coordination structure not having a heteroconjugated ring is disclosed.
  • Patent Document 4 discloses a binuclear metal complex having a coordination structure having a heteroconjugated ring as a metal complex dye from which a photoelectric conversion element having high photoelectric conversion efficiency is obtained.
  • An object of the present invention is to provide a photochemical battery having high photoelectric conversion efficiency and high durability.
  • the present invention relates to the following matters.
  • X N- represents an N-valent anion which is a counter ion (where N is 1 or 2)
  • n represents an integer of 0 to 2.
  • p represents the number of counter ions necessary to neutralize the charge of the complex.
  • the carboxyl group (COOH) may be deprotonated (H + ) to be a carboxy ion (COO ⁇ ).
  • Z + represents N + or P +
  • R 1 , R 2 , R 3 and R 4 may be the same or different, and each independently represents a hydrogen atom or an alkyl group, Or two or more of these together form a saturated or unsaturated heterocycle with the nitrogen or phosphorus atom to which they are attached, and A ⁇ represents an anion.
  • the nitrogen-containing bidentate ligand is 2,2′-bipyridine, 2,2 ′-(4,4′-dimethyl) bipyridine, 2,2 ′-(4,4′-di-t-butyl) bipyridine, 2.
  • the photochemistry according to 1 above which is 2,2 ′-(4,4′-di-n-nonyl) bipyridine, 2,2 ′-(4,4′-di-n-dodecyl) bipyridine or 1,10-phenanthroline. battery.
  • a ammonium salt compound or phosphonium salt compounds - is, tetracyanoborate anion, tetrafluoroborate anion, hexafluorophosphate anion or bis photochemical cell of claim 1, wherein the a (trifluoromethylsulfonyl) imide anion.
  • a photoelectric conversion element in which semiconductor fine particles sensitized by the dinuclear ruthenium complex dye are fixed on an electrode and a counter electrode, and an electrolyte solution layer containing the ammonium salt compound or phosphonium salt compound interposed therebetween 2.
  • the photochemical cell of the present invention comprises semiconductor fine particles sensitized by a dinuclear ruthenium complex dye having a high extinction coefficient and excellent in electron transfer, and an electrolyte solution containing an ammonium salt compound or a phosphonium salt compound.
  • This photochemical battery has high photoelectric conversion efficiency, and high durability can be obtained as compared with a battery not containing an ammonium salt compound or a phosphonium salt compound.
  • the semiconductor fine particles sensitized with the dinuclear ruthenium complex dye of the present invention can be obtained by bringing the dinuclear ruthenium complex and the semiconductor fine particles into contact with each other.
  • the dinuclear ruthenium complex used in the present invention is represented by the general formula (1).
  • X N ⁇ represents an N-valent anion which is a counter ion (where N is 1 or 2).
  • X ⁇ include hexafluorophosphate ion, perchlorate ion, tetraphenylborate ion, tetrafluoroborate ion, trifluoromethanesulfonate ion, thiocyanate ion, sulfate ion, nitrate ion, chloride ion,
  • halide ions such as iodide ions, preferably hexafluorophosphate ions, tetrafluoroborate ions, nitrate ions, halide ions, and more preferably hexafluorophosphate ions, tetrafluoroborate acids.
  • Ions Ions, nitrate ions, and iodide ions.
  • Examples of X 2 ⁇ include sulfate ion, sulfite ion, thiosulfate ion, carbonate ion, monohydrogen phosphate ion, and preferably sulfate ion.
  • the carboxyl group (COOH) may be deprotonated (H + ) to become a carboxy ion (COO ⁇ ).
  • Two nitrogen-containing bidentate ligands having two carboxyl groups are contained in the complex, but they may be the same or different.
  • nitrogen-containing bidentate ligand having two carboxyl groups examples include a ligand represented by the following formula (1-A).
  • R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are each independently a hydrogen atom or a substituted or unsubstituted linear or branched group It represents an alkyl group, or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring with the carbon atom to which they are attached.
  • alkyl group those having 6 or less carbon atoms are preferable, and a methyl group and an ethyl group are more preferable.
  • R 22 and R 23 , R 24 and R 25 , R 21 and R 26 are combined together and a carbon atom to which they are bonded together with a 6-membered aromatic hydrocarbon ring (which may have a substituent) It is also preferable to form.
  • substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
  • R 21 to R 26 are all hydrogen atoms, or R 21 and R 26 are hydrogen atoms, and R 22 and R 23 , R 24 and R 25 are joined together and the 6-membered carbon atom to which they are bonded. It is preferable that an aromatic hydrocarbon ring is formed, and it is particularly preferable that R 21 to R 26 are all hydrogen atoms.
  • nitrogen-containing bidentate ligand having two carboxyl groups examples include 2,2′-bipyridine-4,4′-dicarboxylic acid, 1,10-phenanthroline-4,7-dicarboxylic acid, 2- (2- (4-Carboxypyridyl))-4-carboxyquinoline, 2,2′-biquinoline-4,4′-dicarboxylic acid and the like can be mentioned, and 2,2′-bipyridine-4,4′-dicarboxylic acid is preferable. is there.
  • the carboxyl group (COOH) in these ligands may be deprotonated (H + ) to become a carboxy ion (COO ⁇ ).
  • Examples of the nitrogen-containing tetradentate ligand include a ligand represented by the following formula (1-B1).
  • each of R 31 , R 32 and R 33 independently represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, or two or more of these are combined to form a bond A substituted or unsubstituted aromatic hydrocarbon ring together with the carbon atoms to be represented, and each of R 34 , R 35 and R 36 independently represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group. Or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring with the carbon atom to which they are attached.
  • alkyl group those having 6 or less carbon atoms are preferable, and a methyl group and an ethyl group are more preferable.
  • R 31 to R 36 are joined together to form a 6-membered aromatic hydrocarbon ring (which may have a substituent) together with the carbon atom to which they are bonded.
  • substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
  • R 31 to R 36 are preferably hydrogen atoms or methyl groups, and it is particularly preferable that all of R 31 to R 36 are hydrogen atoms.
  • examples of the nitrogen-containing tetradentate ligand include a ligand represented by the following formula (1-B2).
  • each of R 41 and R 42 independently represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, or a group that is substituted or unsubstituted together with a carbon atom to which they are bonded together.
  • R 43 and R 44 each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, or they are taken together;
  • a substituted or unsubstituted aromatic hydrocarbon ring is formed with the carbon atom to which they are bonded.
  • alkyl group those having 6 or less carbon atoms are preferable, and a methyl group and an ethyl group are more preferable.
  • R 41 and R 42 , R 43 and R 44 together form a 6-membered aromatic hydrocarbon ring (which may have a substituent) together with the carbon atom to which they are bonded. Is also preferable.
  • substituent of the aromatic hydrocarbon ring include an alkyl group (such as a methyl group and an ethyl group) and an alkoxy group (such as a methoxy group and an ethoxy group).
  • R 41 to R 44 are preferably hydrogen atoms or methyl groups, and R 41 to R 44 are particularly preferably all hydrogen atoms.
  • R 41 and R 42 , R 43 and R 44 together form a 6-membered aromatic hydrocarbon ring (which may have a substituent such as a methyl group) together with the carbon atom to which they are bonded.
  • a ligand represented by the following formula (1-B3) is preferable.
  • R 51 , R 52 , R 53 and R 54 each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group
  • R 55 , R 56 , R 57 and R 58 are Each independently represents a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group.
  • alkyl group those having 6 or less carbon atoms are preferable, and a methyl group and an ethyl group are more preferable.
  • R 51 ⁇ R 58 is a hydrogen atom or a methyl group, or R 51 ⁇ R 58 are all hydrogen atoms, R 52, R 53, R 56 and R 57 are methyl groups, R 51, R 54 , R 55 and R 58 are particularly preferably hydrogen atoms, and it is further preferable that R 51 to R 58 are all hydrogen atoms.
  • nitrogen-containing tetradentate ligand examples include 2,2′-bipyrimidine, 2,2′-biimidazole, 2,2′-bibenzimidazole, etc., preferably 2,2′-biimidazole, 2,2′-bibenzimidazole, more preferably 2,2′-bibenzimidazole.
  • Two such nitrogen-containing bidentate ligands are contained in the complex, but they may be the same or different.
  • nitrogen-containing bidentate ligand examples include a ligand represented by the following formula (1-C).
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group, Or two or more of these together form a substituted or unsubstituted aromatic hydrocarbon ring with the carbon atom to which they are attached.
  • the alkyl group has preferably 30 or less carbon atoms, more preferably 18 or less carbon atoms, and more preferably a methyl group, a t-butyl group, a nonyl group, or a dodecyl group.
  • R 11 to R 18 two adjacent R 11 to R 18 , or R 11 and R 18 together, together with the carbon atom to which they are bonded, together with a 6-membered aromatic hydrocarbon ring (which may have a substituent) It is also preferable to form.
  • substituent of the aromatic hydrocarbon ring include an alkyl group (methyl group, t-butyl group, dodecyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.) and the like.
  • R 11 to R 18 are preferably hydrogen atoms or methyl groups, t-butyl groups, nonyl groups, dodecyl groups, R 11 to R 18 are all hydrogen atoms, or R 12 and R 17 are methyl groups, Particularly preferred are t-butyl, nonyl and dodecyl, and R 11 , R 13 to R 16 and R 18 are each preferably a hydrogen atom.
  • R 11 and R 18 are combined to form a 6-membered aromatic hydrocarbon ring (which may have a substituent such as a methyl group) together with the carbon atom to which they are bonded
  • R 12 R 17 is particularly preferably a hydrogen atom or a methyl group, a t-butyl group, a nonyl group, a dodecyl group, more preferably a hydrogen atom.
  • R 13 and R 14 , and R 15 and R 16 together form a 6-membered aromatic hydrocarbon ring (which may have a substituent such as a methyl group) together with the carbon atom to which they are bonded.
  • R 11 , R 12 , R 17 and R 18 are particularly preferably a hydrogen atom or a methyl group, a t-butyl group, a nonyl group, a dodecyl group, more preferably a hydrogen atom.
  • nitrogen-containing bidentate ligand examples include 2,2′-bipyridine, 2,2′-4,4′-dimethyl-bipyridine, and 2,2′-4,4′-di-t-butyl-bipyridine.
  • n represents the valence of the cation and is usually an integer of 0 to 2, preferably 1 or 2, and more preferably 1.
  • P represents the number of counter ions necessary to neutralize the charge of the complex.
  • dinuclear ruthenium complex used in the present invention includes the following compounds (D-1) to (D-18), preferably (D-4) , (D-5), (D-9), (D-10), (D-11), (D-13), (D-16), (D-17) and (D-18) are used. Is done. Note that H of —COOH in formulas (D-1) to (D-18) may be eliminated.
  • dinuclear ruthenium complexes can be synthesized by a known method (for example, see International Publication No. 2006/038587).
  • Examples of the semiconductor fine particles used in the present invention include metal oxides such as titanium oxide, zinc oxide, tin oxide, indium oxide, niobium oxide, tungsten oxide, and vanadium oxide; strontium titanate, calcium titanate, and barium titanate.
  • Compound oxides such as potassium niobate; metal sulfides such as cadmium sulfide and bismuth sulfide; metal selenides such as cadmium selenide; metal tellurides such as cadmium telluride; metal phosphides such as gallium phosphide;
  • metal arsenides such as gallium arsenide are mentioned, metal oxides are preferable, and titanium oxide, zinc oxide, and tin oxide are more preferable.
  • the primary particle size of the semiconductor fine particles is not particularly limited, but those having a particle size of preferably 1 to 5000 nm, more preferably 2 to 500 nm, and particularly preferably 3 to 300 nm are used. These semiconductor fine particles may be used alone or in admixture of two or more.
  • a semiconductor layer semiconductor fine particle film
  • semiconductor fine particles is formed on a conductive support and then immersed in a solution containing the binuclear metal complex dye.
  • the semiconductor layer can be formed by applying a paste of semiconductor fine particles on a conductive support and heating and baking. And after immersing in a pigment
  • Solvents for the dye solution include alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol and ethylene glycol; nitriles such as acetonitrile and propionitrile; N, N-dimethylacetamide, N, N-dimethylformamide and the like Amides; ureas such as N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide, and the like, preferably isopropyl alcohol, t-butanol, and acetonitrile. These organic solvents may be used alone or in combination of two or more.
  • the concentration of the dye in the solution can be determined as appropriate, but since the dye can be adsorbed in a short time, a higher concentration is preferable, and a saturated solution is preferable.
  • the temperature for adsorbing the dye is usually 0 to 80 ° C., preferably 20 to 40 ° C.
  • the time for adsorbing the dye (dipping time in the dye solution) can be appropriately determined, and is, for example, about 1 to 40 hours, preferably about 5 to 20 hours. If the adsorption time is longer than this, the amount of dye adsorbed will not change much, while the photoelectric conversion efficiency may decrease.
  • the photoelectric conversion element of the present invention includes semiconductor fine particles sensitized with a dinuclear ruthenium complex dye. Specifically, for example, the semiconductor fine particles sensitized with the ruthenium complex dye are fixed on an electrode. Is.
  • the electrode is a conductive electrode, preferably a transparent electrode formed on a transparent substrate.
  • the conductive agent include metals such as gold, silver, copper, platinum, and palladium, indium oxide compounds represented by indium oxide (ITO) doped with tin, and tin oxide (FTO) doped with fluorine. Examples thereof include tin oxide compounds and zinc oxide compounds.
  • the photochemical battery of the present invention can be manufactured using semiconductor fine particles sensitized with the above-described dinuclear ruthenium complex dye.
  • the photochemical battery of the present invention specifically has the above-described photoelectric conversion element of the present invention and a counter electrode as electrodes, and an electrolyte solution layer therebetween. Note that at least one of the electrode and the counter electrode used in the photoelectric conversion element of the present invention is a transparent electrode.
  • the counter electrode functions as a positive electrode when combined with a photoelectric conversion element to form a photochemical battery.
  • a substrate having a conductive layer can be used as in the case of the conductive electrode. However, if the metal plate itself is used, the substrate is not necessarily required.
  • the conductive agent used for the counter electrode for example, a conductive metal oxide such as tin oxide doped with a metal such as platinum or carbon or fluorine is preferably used.
  • an electrolyte solution containing an ammonium salt compound or a phosphonium salt compound is used as the electrolyte of the photochemical battery.
  • This electrolyte solution contains an ammonium salt compound or a phosphonium salt compound and a redox pair (redox pair).
  • Ammonium salt compounds or phosphonium salt compounds may be used alone or in combination of two or more. A combination of one or more ammonium salt compounds and one or more phosphonium salt compounds can also be used.
  • ammonium salt compound or phosphonium salt compound used in the present invention has the general formula (2)
  • Z + represents N + or P +
  • R 1 , R 2 , R 3 and R 4 may be the same or different, and are each independently a hydrogen atom or a linear or branched alkyl group. Or two or more of these together form a saturated or unsaturated heterocycle with the nitrogen or phosphorus atom to which they are attached, and A ⁇ represents an anion.
  • a salt having tetracyanoborate, tetrafluoroborate, hexafluorophosphate or bis (trifluoromethylsulfonyl) imide as an anion more preferably a general formula (E)
  • Z + represents N + or P +
  • R 1 , R 2 , R 3, and R 4 may be the same or different, and are each independently a hydrogen atom or a straight chain or A branched alkyl group, or two or more of these together form a saturated or unsaturated heterocycle with the nitrogen or phosphorus atom to which they are attached.
  • a salt having tetracyanoborate as an anion is used.
  • R 1 , R 2 , R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 30 or less carbon atoms, more preferably 18 or less carbon atoms, and particularly preferably 1 to 8 carbon atoms. Further, two adjacent R 1 , R 2 , R 3 and R 4 are combined together with a nitrogen atom or a phosphorus atom to which they are bonded to form a saturated or unsaturated heterocycle, more preferably 6-membered saturated or unsaturated. It is also preferable to form a heterocyclic ring, particularly preferably a piperidine ring.
  • the ammonium cation of the ammonium salt compound in which Z + is N + includes ammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetra Preferred are quaternary ammonium ions such as heptylammonium ion, tetraoctylammonium ion, trimethylhexylammonium ion and trimethyloctylammonium ion, and piperidinium ions such as dimethylpiperidinium ion, dibutylpiperidinium ion and butylmethylpiperidinium ion. More preferred is a quaternary ammonium ion, It is particularly preferred.
  • the phosphonium cation of the phosphonium salt compound in which Z + is P + includes a phosphonium ion, a tetramethylphosphonium ion, a tetraethylphosphonium ion, a tetrapropylphosphonium ion, a tetrabutylphosphonium ion, a tetrapentylphosphonium ion, a tetrahexylphosphonium ion, a tetra Quaternary phosphonium ions such as heptylphosphonium ion, tetraoctylphosphonium ion, trimethylhexylphosphonium ion, and trimethyloctylphosphonium ion are preferred, quaternary phosphonium ions are more preferred, and tetrabutylphosphonium ions are particularly preferred.
  • the concentration of the ammonium salt compound and / or phosphonium salt compound used in the present invention in the electrolyte solution is preferably in the range of 0.001 mol / l to saturation concentration, more preferably in the range of 0.1 mol / l to saturation concentration. 5 mol / l to 5 mol / l is particularly preferred.
  • the electrolyte solution of the present invention preferably contains a redox pair (redox pair).
  • the redox pair to be used is not particularly limited.
  • (1) iodine and iodide for example, metal iodides such as lithium iodide and potassium iodide; quaternary ammonium compounds such as tetrabutylammonium iodide, tetrapropylammonium iodide, pyridinium iodide and imidazolium iodide) (Iodide) combinations
  • Bromine and bromides for example, metal bromides such as lithium bromide and potassium bromide; bromides of quaternary ammonium compounds such as tetrabutylammonium bromide, tetrapropylammonium bromide, pyridinium bromide and imidazolium bromide
  • a combination of (3) Combination of chlorine and chloride for example, metal chloride
  • Porphyrin-based compounds can be mentioned, and preferably the redox couples mentioned in (1) above are used. In addition, you may use these redox pairs individually or in mixture of 2 or more types. The amount of use of these redox pairs can be determined as appropriate.
  • the solvent for the electrolyte solution examples include water, alcohols, nitriles, chain ethers, cyclic ethers, chain esters, cyclic esters, chain amides, cyclic amides, chain sulfones, cyclic Sulfones, chain ureas, cyclic ureas, amines and the like are used.
  • the solvent of electrolyte solution is not limited to these, It can use individually or in mixture of 2 or more types.
  • the photochemical cell of the present invention can be manufactured by a conventionally applied method, for example, (1) A semiconductor fine particle paste such as an oxide is applied on a transparent electrode and heated and fired to produce a thin film of semiconductor fine particles. (2) Next, when the thin film of semiconductor fine particles is titania, baking is performed at a temperature of 400 to 550 ° C. for 0.5 to 1 hour. (3) The transparent electrode with the obtained thin film is immersed in a dye solution, and a dinuclear ruthenium complex dye is supported to produce a photoelectric conversion element. (4) The obtained photoelectric conversion element is combined with a transparent electrode on which platinum or carbon is vapor-deposited as a counter electrode, and an electrolyte solution is put therebetween.
  • the photochemical battery of the present invention can be manufactured by performing the operation described above.
  • the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
  • the photoelectric conversion efficiency of the photochemical cell was measured by irradiating simulated sunlight from a solar simulator (manufactured by Eihiro Seiki Co., Ltd.).
  • the binuclear ruthenium complex dye was synthesized with reference to International Publication No. 2006/038587.
  • Example 1 Preparation of porous titania electrode
  • a transparent layer Using titania paste PST-18NR (manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a transparent layer and PST-400C (manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a diffusion layer, on a transparent conductive glass electrode (manufactured by Asahi Glass Co., Ltd.) It was applied using a screen printer.
  • the obtained film was aged for 5 minutes in an atmosphere of 25 ° C. and a relative humidity of 60%, and the aged film was baked at 440 to 460 ° C. for 30 minutes. By repeating this operation, a 16 mm 2 porous titania electrode was produced.
  • the porous titania electrode was immersed in the saturated dye solution in an incubator with an internal temperature of 30 ° C. for 20 hours to produce a porous titania electrode adsorbing the dye.
  • the photoelectric conversion efficiency of the obtained photochemical battery was measured by irradiating 100 mW / cm 2 of artificial sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd.
  • the obtained photochemical battery was allowed to stand in a dark place at 60 ° C. for a predetermined time, then returned to room temperature, and the photoelectric conversion efficiency ( ⁇ ) was changed to 100 mW / cm 2 of pseudo-sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd. Irradiated and measured.
  • Table 1 shows the maintenance ratio of the photoelectric conversion efficiency after 5 days when the photoelectric conversion efficiency after 1 day in the dark at 60 ° C. is defined as 100%.
  • Examples 2-6, Comparative Examples 1-2 A photochemical battery was prepared in the same manner as in Example 1 except that the dinuclear ruthenium complex dye, the dye solution concentration, and the type and concentration of the additive in the electrolyte solution were changed, and the photoelectric conversion efficiency was measured.
  • the dye solution concentration of the dinuclear ruthenium complex dye (D-18) was 0.3 mmol / l.
  • the results are also shown in Table 1.
  • 4-t-butylpyridine (TBP) is a compound known as an additive that gives the best results.
  • Examples 7 to 10 A photochemical battery was prepared in the same manner as in Example 2 except that tetrabutylammonium tetracyanoborate, which is an additive in the electrolyte solution, was changed to the additive shown in Table 2, and the photoelectric conversion efficiency was measured. The results are also shown in Table 2.
  • Examples 11 to 17 A photochemical cell was prepared in the same manner as in Example 6 except that 1-methyl-3-propylimidazolium iodide (MPI-I), which is an iodide in the electrolyte solution, was changed to the iodide shown in Table 3. Conversion efficiency was measured. The results are also shown in Table 3.
  • MPI-I 1-methyl-3-propylimidazolium iodide
  • Example 18 (Preparation of porous titania electrode) Using titania paste PST-18NR (manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a transparent layer and PST-400C (manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a diffusion layer, on a transparent conductive glass electrode (manufactured by Asahi Glass Co., Ltd.) It was applied using a screen printer. The obtained film was aged for 5 minutes in an atmosphere of 25 ° C. and a relative humidity of 60%, and the aged film was baked at 440 to 460 ° C. for 30 minutes. By repeating this operation, a 16 mm 2 porous titania electrode was produced.
  • the photoelectric conversion efficiency of the obtained photochemical battery was measured by irradiating 100 mW / cm 2 of artificial sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd.
  • the obtained photochemical battery was allowed to stand in a dark place at 60 ° C. for a predetermined time, then returned to room temperature, and the photoelectric conversion efficiency ( ⁇ ) was changed to 100 mW / cm 2 of pseudo-sunlight using a solar simulator manufactured by Eihiro Seiki Co., Ltd. Irradiated and measured.
  • Table 4 shows the maintenance ratio of the photoelectric conversion efficiency after 5 days when the photoelectric conversion efficiency after 1 day in the dark at 60 ° C. is defined as 100%.
  • Comparative Examples 3-4 A photochemical battery was produced in the same manner as in Example 18 except that the kind and concentration of the additive in the electrolyte solution were changed, and the photoelectric conversion efficiency was measured. The results are also shown in Table 4. 4-t-butylpyridine (TBP) is a compound known as an additive that gives the best results.
  • the semiconductor fine particles sensitized by a dinuclear ruthenium complex dye having a high extinction coefficient and excellent in electron transfer, and an electrolyte solution containing an ammonium salt compound or a phosphonium salt compound have high durability.
  • a photochemical battery can be provided.

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Abstract

L'invention concerne une cellule photochimique qui comprend : des particules semi-conductrices fines qui sont sensibilisées par un colorant à complexe de ruthénium binucléaire ; et une solution d'électrolyse qui contient un composé de sel d'ammonium ou un composé de sel de phosphonium.
PCT/JP2011/050572 2010-01-15 2011-01-14 Cellule photochimique comprenant des particules semi-conductrices fines sensibilisées par un colorant à complexe de ruthénium binucléaire et solution d'électrolyse contenant un composé de sel d'ammonium ou un composé de sel de phosphonium Ceased WO2011087099A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012114315A1 (fr) * 2011-02-25 2012-08-30 Ecole Polytechnique Federale De Lausanne (Epfl) Couple redox amélioré pour des dispositifs électrochimiques et optoélectroniques
JP2014044805A (ja) * 2012-08-24 2014-03-13 Osaka Gas Co Ltd 電解液及び光電変換素子

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004227920A (ja) * 2003-01-23 2004-08-12 Toshiba Corp 光増感型太陽電池
WO2006077893A1 (fr) * 2005-01-12 2006-07-27 Otsuka Chemical Co., Ltd. Solution electrolytique et dispositif electrochimique
JP2006332469A (ja) * 2005-05-27 2006-12-07 Peccell Technologies Inc 光充電可能な積層型キャパシタ
JP2007306017A (ja) * 2003-07-01 2007-11-22 Otsuka Chemical Co Ltd 第４級アンモニウム塩を含む電解液並びに電気化学デバイス
WO2008153184A1 (fr) * 2007-06-14 2008-12-18 Ube Industries, Ltd. Cellule photochimique comprenant des particules de semi-conducteur rendues photosensibles par un colorant de type complexe binucléaire du ruthénium et une solution d'électrolyte contenant principalement un liquide ionique
WO2009069757A1 (fr) * 2007-11-30 2009-06-04 Fujikura Ltd. Composition électrolytique et élément de conversion photoélectrique l'utilisant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004227920A (ja) * 2003-01-23 2004-08-12 Toshiba Corp 光増感型太陽電池
JP2007306017A (ja) * 2003-07-01 2007-11-22 Otsuka Chemical Co Ltd 第４級アンモニウム塩を含む電解液並びに電気化学デバイス
WO2006077893A1 (fr) * 2005-01-12 2006-07-27 Otsuka Chemical Co., Ltd. Solution electrolytique et dispositif electrochimique
JP2006332469A (ja) * 2005-05-27 2006-12-07 Peccell Technologies Inc 光充電可能な積層型キャパシタ
WO2008153184A1 (fr) * 2007-06-14 2008-12-18 Ube Industries, Ltd. Cellule photochimique comprenant des particules de semi-conducteur rendues photosensibles par un colorant de type complexe binucléaire du ruthénium et une solution d'électrolyte contenant principalement un liquide ionique
WO2009069757A1 (fr) * 2007-11-30 2009-06-04 Fujikura Ltd. Composition électrolytique et élément de conversion photoélectrique l'utilisant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012114315A1 (fr) * 2011-02-25 2012-08-30 Ecole Polytechnique Federale De Lausanne (Epfl) Couple redox amélioré pour des dispositifs électrochimiques et optoélectroniques
JP2014044805A (ja) * 2012-08-24 2014-03-13 Osaka Gas Co Ltd 電解液及び光電変換素子

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