WO2015190608A1 - Élément de cellule solaire à colorant - Google Patents

Élément de cellule solaire à colorant Download PDF

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WO2015190608A1
WO2015190608A1 PCT/JP2015/067059 JP2015067059W WO2015190608A1 WO 2015190608 A1 WO2015190608 A1 WO 2015190608A1 JP 2015067059 W JP2015067059 W JP 2015067059W WO 2015190608 A1 WO2015190608 A1 WO 2015190608A1
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dye
solar cell
sensitized solar
group
oxide semiconductor
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PCT/JP2015/067059
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Japanese (ja)
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健治 勝亦
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株式会社フジクラ
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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
    • 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-sensitized solar cell element.
  • a dye-sensitized solar cell element As a photoelectric conversion element, a dye-sensitized solar cell element has attracted attention because it is inexpensive and high photoelectric conversion efficiency can be obtained, and various developments have been made regarding the dye-sensitized solar cell element.
  • the dye-sensitized solar cell element generally includes at least one dye-sensitized solar cell, and the dye-sensitized solar cell includes a working electrode, a counter electrode, and an electrolyte provided between the working electrode and the counter electrode.
  • the working electrode has an oxide semiconductor layer, and a photosensitizing dye is adsorbed to the oxide semiconductor layer.
  • Patent Document 1 discloses a dye-sensitized solar cell in which a dye is adsorbed on a porous semiconductor layer by immersing a glass substrate provided with the porous semiconductor layer in a solution containing a photosensitizing dye for 24 hours. ing.
  • This invention is made
  • the present inventor has intensively studied to solve the above problems. As a result, the inventor is in a state where no more photosensitizing dye can be adsorbed to the oxide semiconductor layer, that is, the adsorption amount of the photosensitizing dye to the oxide semiconductor layer is in a saturated state, I thought it might be the cause of the above problems. In other words, the present inventor may unexpectedly be able to sufficiently improve the photoelectric conversion characteristics by making the adsorption amount of the photosensitizing dye to the oxide semiconductor layer non-saturated. Thought. Therefore, as a result of further earnest research, the present inventor has found that the above-described problems can be solved by the following invention.
  • the present invention includes at least one dye-sensitized solar cell, and the dye-sensitized solar cell includes a first electrode, a second electrode facing the first electrode, and the first electrode or the second electrode.
  • An oxide semiconductor layer provided on the first electrode, an electrolyte provided between the first electrode and the second electrode, and a photosensitizing dye adsorbed on the oxide semiconductor layer.
  • Coverage m / m sat (In the above formula, m represents the adsorption amount (unit: mol / cm 2 ) of the photosensitizing dye to the oxide semiconductor layer, and m sat represents the saturated adsorption of the photosensitizing dye to the oxide semiconductor layer.
  • a dye-sensitized solar cell element having a coverage defined by the amount (unit: mol / cm 2 )) of 0.80 to 0.98.
  • the photoelectric conversion characteristics can be sufficiently improved as compared with the case where the coverage is out of the above range.
  • the photosensitizing dye is composed of a ruthenium metal complex
  • the ruthenium metal complex includes a central metal composed of ruthenium and a ligand coordinated to the central metal
  • the ligand includes a bipyridine derivative obtained by substituting a hydrogen atom of bipyridine with a substituent, or a terpyridine derivative obtained by substituting a hydrogen atom of terpyridine with a substituent.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell element can be particularly improved.
  • the ligand includes a first ligand made of the bipyridine derivative or the terpyridine derivative and a second ligand coordinated to the central metal, and the second
  • the ligand is represented by the following general formula (1) and is coordinated to the central metal with two oxygen atoms, represented by a halogen group, —CN, —NCS, —NCO, substituted or unsubstituted pyridine It is preferably composed of at least one selected from the group consisting of ⁇ -diketonate ligands.
  • Y 1 and Y 2 each independently represent a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms or —CH ⁇ CHY 3.
  • Y 3 represents a substituted or unsubstituted aryl group. Represents.
  • the substituents of the bipyridine derivative and the terpyridine derivative are substituted or unsubstituted aliphatic hydrocarbon groups having 3 to 20 carbon atoms, alkoxy groups having 3 to 20 carbon atoms, carbon numbers 3 to 20 thioalkoxy groups, a group represented by the following general formula (A), a group represented by the following general formula (B), a group represented by the following general formula (C), and the following general formula (D It is preferable to represent at least one selected from the group consisting of groups represented by: (In the above formulas (A) to (C), X 1 represents a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms.
  • X 2 and X 3 are each independently a hydrogen atom or a substituted group having 1 to 9 carbon atoms. Or an unsubstituted alkyl group, an alkoxy group, or a thioalkoxy group, X 2 and X 3 may combine with each other to form a heterocycle, m represents an integer of 1 to 3, and the above formula ( In D), Z 1 represents a monovalent cation or a methyl group.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell element can be further improved.
  • the dye-sensitized solar cell further includes a co-adsorbent adsorbed on the oxide semiconductor layer, and the co-adsorbent is an organic compound represented by the following general formula (2). It is preferably composed of a compound or a salt thereof. (In the above formula (2), n represents an integer of 0 to 5, and R 1 represents a monovalent group having a steroid skeleton.)
  • the monovalent group having the steroid skeleton is specifically a monovalent group represented by the following general formula (3).
  • R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydroxyl group.
  • the molar ratio of the co-adsorbent to the photosensitizing dye is preferably 0.5 to 200.
  • the leakage current can be more effectively reduced and the generated current can be further increased as compared with a case outside the above range. it can.
  • the adsorption amount m of the photosensitizing dye is preferably 0.5 ⁇ 10 ⁇ 7 to 3.0 ⁇ 10 ⁇ 7 mol / cm 2 .
  • the photoelectric conversion characteristics of the dye-sensitized solar cell element can be particularly improved as compared with the case where the adsorption amount m of the photosensitizing dye is out of the above range.
  • saturated adsorption amount of photosensitizing dye to oxide semiconductor layer m sat is the value obtained when the oxide semiconductor layer is immersed in a dye solution containing 0.3 mM photosensitizing dye. It is the molar amount of the photosensitizing dye adsorbed per 1 cm 2 of the surface of the physical semiconductor layer, and is a value calculated as follows. That is, the dye adsorption amount x of the oxide semiconductor layer in which the photosensitizing dye is adsorbed at different dye adsorption times t is measured, and the dye adsorption amount x with respect to the dye adsorption time t is plotted.
  • the obtained dye adsorption amount x is fitted to the following equation to determine the constants a and b.
  • the dye adsorption amount x at the dye adsorption time when the increase rate ⁇ represented by the following formula is 0.01 is obtained.
  • this dye adsorption amount x is calculated as the saturated dye adsorption amount m sat .
  • a dye-sensitized solar cell element capable of sufficiently improving photoelectric conversion characteristics is provided.
  • FIG. 1 is a cross-sectional view showing an embodiment of the dye-sensitized solar cell element of the present invention.
  • the dye-sensitized solar cell element 100 includes one dye-sensitized solar cell 50, and the dye-sensitized solar cell 50 has a transparent conductive substrate 15 that is a first electrode. 10, a counter electrode 20 as a second electrode facing the transparent conductive substrate 15 of the working electrode 10, and an annular sealing portion 30 connecting the working electrode 10 and the counter electrode 20.
  • a cell space formed by the transparent conductive substrate 15, the counter electrode 20, and the sealing portion 30 of the working electrode 10 is filled with an electrolyte 40.
  • the counter electrode 20 includes a conductive substrate 21 and a catalyst layer 22 provided on the working electrode 10 side of the conductive substrate 21 and contributing to the reduction of the electrolyte 40.
  • the working electrode 10 includes a transparent conductive substrate 15 and at least one oxide semiconductor layer 13 provided on the transparent conductive film 12 of the transparent conductive substrate 15.
  • the transparent conductive substrate 15 includes a transparent substrate 11 and a transparent conductive film 12 provided on the transparent substrate 11.
  • the oxide semiconductor layer 13 is disposed inside the sealing portion 30. Further, both the photosensitizing dye and the co-adsorbent are adsorbed on the oxide semiconductor layer 13. The co-adsorbent is for suppressing association of photosensitizing dyes.
  • Coverage m / m sat (In the above formula, m represents the adsorption amount of the photosensitizing dye to the oxide semiconductor layer 13 (unit: mol / cm 2 ), and m sat represents the saturated adsorption amount of the photosensitizing dye to the oxide semiconductor layer 13 ( The coverage defined by the unit: mol / cm 2 )) is 0.80 to 0.98.
  • the photoelectric conversion characteristics can be sufficiently improved as compared with the case where the coverage is out of the above range.
  • the working electrode 10 includes the transparent conductive substrate 15 and at least one oxide semiconductor layer 13 provided on the transparent conductive substrate 15.
  • the transparent conductive substrate 15 includes a transparent substrate 11 and a transparent conductive film 12 provided on the transparent substrate 11.
  • the material which comprises the transparent substrate 11 should just be a transparent material, for example, as such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), and polyethersulfone (PES).
  • PET polyethylene terephthalate
  • PEN Polyethylene naphthalate
  • PC polycarbonate
  • PES polyethersulfone
  • the thickness of the transparent substrate 11 is appropriately determined according to the size of the dye-sensitized solar cell element 100 and is not particularly limited, but may be in the range of 50 to 40,000 ⁇ m, for example.
  • the material constituting the transparent conductive film 12 examples include conductive metal oxides such as tin-added indium oxide (ITO), tin oxide (SnO 2 ), and fluorine-added tin oxide (FTO).
  • the transparent conductive film 12 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 12 is composed of a single layer, the transparent conductive film 12 is preferably composed of FTO because it has high heat resistance and chemical resistance.
  • the thickness of the transparent conductive film 12 may be in the range of 0.01 to 2 ⁇ m, for example.
  • the oxide semiconductor layer 13 is composed of oxide semiconductor particles.
  • the oxide semiconductor particles include titanium oxide (TiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), strontium titanate (SrTiO 3 ), and tin oxide (SnO 2 ).
  • the thickness of the oxide semiconductor layer 13 may be 0.1 to 100 ⁇ m, for example.
  • the counter electrode 20 includes the conductive substrate 21 and the conductive catalyst layer 22 provided on the working electrode 10 side of the conductive substrate 21 and contributing to the reduction of the electrolyte 40.
  • the conductive substrate 21 is formed by forming a film made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless steel, or a film made of a conductive oxide such as ITO or FTO on the transparent substrate 11 described above. Consists of.
  • the thickness of the conductive substrate 21 is appropriately determined according to the size of the dye-sensitized solar cell element 100 and is not particularly limited, but may be, for example, 0.005 to 4 mm.
  • the catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like.
  • carbon nanotubes are suitably used as the carbon-based material.
  • sealing portion 30 examples include thermoplastic resins such as modified polyolefin resins and vinyl alcohol polymers, and resins such as ultraviolet curable resins.
  • modified polyolefin resins include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, and ethylene-vinyl alcohol copolymers. These resins can be used alone or in combination of two or more.
  • the electrolyte 40 includes a redox couple such as I ⁇ / I 3 ⁇ and an organic solvent.
  • organic solvents include acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, ⁇ -butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used.
  • the electrolyte 40 may use an ionic liquid instead of the organic solvent.
  • the ionic liquid for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used.
  • room temperature molten salts examples include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, dimethylimidazolium iodide, ethylmethylimidazolium iodide, and dimethylpropyl.
  • Imidazolium iodide, butylmethylimidazolium iodide, or methylpropyl imidazolium iodide is preferably used.
  • the electrolyte 40 may be a mixture of the ionic liquid and the organic solvent instead of the organic solvent.
  • An additive can be added to the electrolyte 40.
  • the additive include LiI, I 2 , 4-t-butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butylbenzimidazole and the like.
  • a nano-composite gel electrolyte which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO 2 , TiO 2 , carbon nanotubes, etc. into the electrolyte, may be used, and polyvinylidene fluoride may be used.
  • an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.
  • the photosensitizing dye is not particularly limited, and is composed of a ruthenium metal complex.
  • the ruthenium metal complex includes a central metal composed of ruthenium and a ligand coordinated to the central metal.
  • the child preferably contains a bipyridine derivative obtained by substituting a hydrogen atom of bipyridine with a substituent, or a terpyridine derivative obtained by substituting a hydrogen atom of terpyridine with a substituent.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell element 100 can be particularly improved.
  • the substituents of the bipyridine derivative and terpyridine derivative are substituted or unsubstituted aliphatic hydrocarbon groups having 3 to 20 carbon atoms, alkoxy groups having 3 to 20 carbon atoms, thioalkoxy groups having 3 to 20 carbon atoms, and the following general formula ( A), a group represented by the following general formula (B), a group represented by the following general formula (C), and a group represented by the following general formula (D). It is preferable to represent at least one.
  • X 1 represents a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms.
  • X 2 and X 3 are each independently a hydrogen atom or a substituted group having 1 to 9 carbon atoms. Or an unsubstituted alkyl group, an alkoxy group, or a thioalkoxy group, X 2 and X 3 may combine with each other to form a heterocycle, m represents an integer of 1 to 3, and the above formula ( In D), Z 1 represents a monovalent cation or a methyl group.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell element 100 can be further improved.
  • Examples of the aliphatic hydrocarbon group constituting the substituent of the bipyridine derivative and terpyridine derivative include an alkyl group.
  • examples of the substituent of the alkyl group include a halogen group, a nitro group, and an alkoxy group having 1 to 6 carbon atoms.
  • the heterocycle formed by the bond of X 2 and X 3 is a ring having a hetero atom, and examples of the hetero atom include an oxygen atom, a nitrogen atom and a sulfur atom. It is done.
  • the heterocycle having an oxygen atom include dioxolane and dioxane.
  • X 2 and X 3 are each composed of —OCH 2 —.
  • the heterocycle having a nitrogen atom include piperidine and piperazine.
  • Examples of the heterocycle having a sulfur atom include pentamethylene sulfide.
  • Specific examples of the group represented by the general formula (B) include groups represented by the following structural formulas (B1) to (B3).
  • Examples of the monovalent cation represented by Z 1 in the above formula (D) include a hydrogen ion, an ammonium ion, and a sodium ion. Of these, Z 1 is preferably a hydrogen ion. In this case, the photosensitizing dye can be produced easily and inexpensively.
  • the ligand includes a first ligand composed of the bipyridine derivative or the terpyridine derivative and a second ligand coordinated to a central metal, and the second ligand is a halogen group, —CN, Selected from the group consisting of —NCS, —NCO, substituted or unsubstituted pyridine, and ⁇ -diketonate ligand represented by the following general formula (1) and coordinated to the central metal at two oxygen atoms It is preferable to be composed of at least one kind.
  • Y 1 and Y 2 each independently represent a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms or —CH ⁇ CHY 3.
  • Y 3 represents a substituted or unsubstituted aryl group. Represents.
  • examples of the substituent of the alkyl group constituting Y 1 and Y 2 include a halogen group, a nitro group, and an alkoxy group having 1 to 9 carbon atoms.
  • examples of the aryl group constituting Y 3 include a phenyl group and a naphthyl group.
  • examples of the substituent for the aryl group include a hydroxyl group and an alkyl group having 1 to 9 carbon atoms.
  • examples of the substituent of the pyridine include aliphatic hydrocarbon groups such as a carboxyl group and an alkyl group.
  • the coverage is more preferably 0.82 to 0.95, and still more preferably 0.89 to 0.95.
  • the adsorption amount m (unit: mol / cm 2 ) of the photosensitizing dye is not particularly limited, but is preferably 0.5 ⁇ 10 ⁇ 7 to since the photoelectric conversion characteristics can be particularly improved. It is 3.0 ⁇ 10 ⁇ 7 mol / cm 2 , more preferably 0.7 ⁇ 10 ⁇ 7 to 1.5 ⁇ 10 ⁇ 7 mol / cm 2 .
  • the coadsorbent is not particularly limited as long as it suppresses the association of the photosensitizing dyes.
  • an organic compound represented by the following general formula (2) or a salt thereof may be used as the coadsorbent.
  • the organic compound is composed of only nonmetallic atoms.
  • n represents an integer of 0 to 5
  • R 1 represents a monovalent group having a steroid skeleton.
  • N is preferably an integer of 0-2.
  • a monovalent group having a steroid skeleton for example, a monovalent group represented by the following general formula (3) is used.
  • R ⁇ 2 >, R ⁇ 3 > and R ⁇ 4 > represent a hydrogen atom or a hydroxyl group each independently.
  • coadsorbent having a steroid skeleton examples include deoxycholic acid, chenodeoxycholic acid, cholic acid, hyodeoxycholic acid, and salts thereof.
  • the molar ratio of the coadsorbent to the photosensitizing dye is usually 0.5 to 200, preferably 10 to 100, more preferably 60 to 100.
  • the leakage current can be more effectively reduced and the generated current can be further increased as compared with a case outside the above range. it can.
  • a transparent conductive substrate 15 formed by forming a transparent conductive film 12 on one transparent substrate 11 is prepared.
  • a sputtering method As a method for forming the transparent conductive film 12, a sputtering method, a vapor deposition method, a spray pyrolysis method, a CVD method, or the like is used.
  • an oxide semiconductor layer 13 is formed on the transparent conductive film 12.
  • the oxide semiconductor layer 13 is formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles, followed by firing.
  • the oxide semiconductor layer forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles described above.
  • a method for printing the oxide semiconductor layer forming paste for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.
  • the firing temperature varies depending on the material of the oxide semiconductor particles, but is usually 350 to 600 ° C.
  • the firing time also varies depending on the material of the oxide semiconductor particles, but is usually 1 to 5 hours.
  • the photosensitizing dye synthesized as described above is adsorbed on the surface of the oxide semiconductor layer 13 of the working electrode 10.
  • the working electrode 10 is immersed in a solution containing a photosensitizing dye, the photosensitizing dye is adsorbed on the oxide semiconductor layer 13, and then the excess photosensitizer is added with the solvent component of the solution.
  • the photosensitizing dye may be adsorbed to the oxide semiconductor layer 13 by washing away the dye and drying it. At this time, the photosensitizing dye is adsorbed on the oxide semiconductor layer 13 so that the coverage is 0.80 to 0.98.
  • the adsorption amount m of the photosensitizing dye adsorbed on the oxide semiconductor layer 13 is 0.80 to 0.98 of the saturated adsorption amount m sat of the photosensitizing dye adsorbed on the oxide semiconductor layer 13.
  • the photosensitizing dye is adsorbed on the oxide semiconductor layer 13.
  • coating the solution containing a photosensitizing dye to the oxide semiconductor layer 13 you may make a photosensitizing dye adsorb
  • the above-described co-adsorbent is adsorbed on the surface of the oxide semiconductor layer 13 of the working electrode 10.
  • the working electrode 10 is immersed in a solution containing a co-adsorbent, the co-adsorbent is adsorbed on the oxide semiconductor layer 13, and then the extra co-adsorbent is removed with the solvent component of the solution.
  • the co-adsorbent may be adsorbed on the surface of the oxide semiconductor layer 13 by washing and drying.
  • the coadsorbent may be adsorbed to the oxide semiconductor layer 13 by applying a solution containing the coadsorbent to the oxide semiconductor layer 13 and then drying the solution.
  • the co-adsorbent is adsorbed on the surface of the oxide semiconductor layer 13 in a region where the photosensitizing dye is not adsorbed.
  • the co-adsorbent may be mixed with the photosensitizing dye and simultaneously adsorbed on the surface of the oxide semiconductor layer 13.
  • the oxide semiconductor layer 13 may be immersed in a solution containing a photosensitizing dye and a coadsorbent.
  • the electrolyte 40 is disposed on the oxide semiconductor layer 13.
  • the electrolyte 40 can be disposed by a printing method such as screen printing.
  • the sealing part forming body can be obtained, for example, by preparing a sealing resin film and forming one rectangular opening in the sealing resin film.
  • the sealing portion forming body is bonded onto the working electrode 10.
  • adhesion of the sealing portion forming body to the working electrode 10 can be performed by, for example, heating and melting the sealing portion forming body.
  • the sealing portion forming body may be bonded to the counter electrode 20 in advance, and the sealing portion forming body may be bonded to the sealing portion forming body on the working electrode 10 side.
  • Lamination of the counter electrode 20 to the sealing portion forming body may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure.
  • the dye-sensitized solar cell element 100 including one dye-sensitized solar cell 50 is obtained.
  • the present invention is not limited to the above embodiment.
  • the porous oxide semiconductor layer 13 is provided on the transparent conductive film 12 of the transparent conductive substrate 15, and the dye-sensitized solar cell element 100 receives light from the transparent conductive substrate 15 side.
  • the dye-sensitized solar cell element uses an opaque material (for example, a metal substrate) for the base material on which the porous oxide semiconductor layer 13 is formed, and is transparent on the base material on which the counter electrode 20 is formed.
  • the material may have a structure in which light is incident from the counter electrode side, and the dye-sensitized solar cell element may have a structure in which light is incident from both sides.
  • the coadsorbent is adsorbed on the surface of the oxide semiconductor layer 13 of the working electrode 10, but the coadsorbent may not necessarily be used.
  • the dye-sensitized solar cell element is configured by one dye-sensitized solar cell 50, but the dye-sensitized solar cell element may include a plurality of dye-sensitized solar cells 50.
  • a transparent conductive substrate was prepared by forming a transparent conductive film made of FTO having a thickness of 1 ⁇ m on a transparent substrate made of glass having a thickness of 1 mm.
  • an oxide semiconductor layer forming paste containing titania was applied onto the transparent conductive film, dried, and then fired at 500 ° C. for 1 hour.
  • a working electrode having a porous oxide semiconductor layer having a thickness of 20 ⁇ m was obtained.
  • the dye solution is cis-di (thiocyanato)-(2,2′-bipyridyl-4,4′-dicarboxylic acid) (4,4′-dinonyl-2,2′-bipyridyl)-in 1-propanol solvent. It was prepared by dissolving a photosensitizing dye composed of ruthenium (II) (hereinafter referred to as “Z907”) to a concentration of 0.3 mM.
  • ruthenium (II) hereinafter referred to as “Z907”
  • the flow rate of the dye solution in the direction parallel to the surface of the oxide semiconductor layer of the working electrode was set to 0 cm / min.
  • the adsorption amount m of the photosensitizing dye with respect to the oxide semiconductor layer was adjusted as shown in Table 1, and the coverage was adjusted as shown in Table 1.
  • Electrolyte in a solvent consisting of acetonitrile was prepared by dissolving lithium iodide so as 2.0 M, the I 2 and 0.05 M.
  • the sealing portion forming body is prepared by preparing a single sealing resin film made of 10 mm ⁇ 10 mm ⁇ 50 ⁇ m ionomer (trade name: High Milan, Mitsui / DuPont Polychemical Co., Ltd.) Obtained by forming a square opening. At this time, the opening had a size of 6 mm ⁇ 6 mm ⁇ 50 ⁇ m.
  • a counter electrode was prepared.
  • the counter electrode was prepared by forming a catalyst layer made of platinum having a thickness of 600 nm on a 15 mm ⁇ 15 mm ⁇ 1 mm FTO conductive glass substrate by sputtering. Further, another sealing part forming body was prepared, and this sealing part forming body was adhered to the surface of the counter electrode facing the working electrode in the same manner as described above.
  • the sealing portion forming body bonded to the working electrode and the sealing portion forming body bonded to the counter electrode were opposed to each other, and the sealing portion forming bodies were overlapped with each other. And in this state, the sealing part forming body was heated and melted while being pressurized. Thus, a sealing portion was formed between the working electrode and the counter electrode.
  • Example 4 to 5 and Comparative Examples 5 to 6 While the working electrode is immersed in the dye solution, the flow rate of the dye solution in the direction parallel to the surface of the oxide semiconductor layer of the working electrode is set to 0.1 cm / min, and the dye with respect to the dye adsorption time shown in Table 2 is used.
  • a dye-sensitized solar cell element was produced in the same manner as in Example 1 except that the adsorption amount m and the coverage were as shown in Table 2.
  • Example 6 to 8 and Comparative Example 7 While the working electrode is immersed in the dye solution, the flow rate of the dye solution in the direction parallel to the surface of the oxide semiconductor layer of the working electrode is set to 1.2 cm / min, and the dye with respect to the dye adsorption time shown in Table 3 is used.
  • a dye-sensitized solar cell element was produced in the same manner as in Example 1 except that the adsorption amount m and the coverage were as shown in Table 3.
  • Example 9 Deoxycholic acid (hereinafter referred to as “DCA”) as a co-adsorbent is added to the dye solution so that the concentration of DCA in the dye solution is 20 mM, and the dye adsorption amount m with respect to the dye adsorption time shown in Table 4 and A dye-sensitized solar cell element was produced in the same manner as in Example 1 except that the coverage was as shown in Table 4.
  • DCA Deoxycholic acid
  • Example 11 and Comparative Examples 12 to 13 DCA as a co-adsorbent was added to the dye solution so that the concentration of DCA in the dye solution was 20 mM, and the dye adsorption amount m and the coverage with respect to the dye adsorption time shown in Table 6 were as shown in Table 6. Except for the above, a dye-sensitized solar cell element was produced in the same manner as in Example 1.
  • the photoelectric conversion characteristics can be sufficiently improved.

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Abstract

L'invention concerne un élément de cellule solaire à colorant qui comporte au moins une cellule solaire à colorant. La cellule solaire à colorant comporte : une première électrode ; une deuxième électrode qui est orientée vers la première électrode ; une couche de semiconducteur à l'oxyde qui est mise en œuvre sur la première électrode ou la deuxième électrode ; un électrolyte qui est mis en œuvre entre la première électrode et la deuxième électrode ; et un colorant photosensibilisant qui est adsorbé sur la couche de semiconducteur à l'oxyde. En ce qui concerne cet élément de cellule solaire à colorant, la couverture définie par la formule ci-dessous est comprise entre 0,80 et 0,98. Couverture = m/msat (dans la formule, m représente la quantité d'adsorption (unité : mol/cm2) du colorant photosensibilisant sur la couche de semiconducteur à l'oxyde ; et msat représente la quantité d'absorption par saturation (unité : mol/cm2) du colorant photosensibilisant sur la couche de semiconducteur à l'oxyde.)
PCT/JP2015/067059 2014-06-13 2015-06-12 Élément de cellule solaire à colorant WO2015190608A1 (fr)

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