WO2014162641A1 - Électrolyte pour cellule solaire sensibilisée par colorant et cellule solaire sensibilisée par colorant - Google Patents

Électrolyte pour cellule solaire sensibilisée par colorant et cellule solaire sensibilisée par colorant Download PDF

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Publication number
WO2014162641A1
WO2014162641A1 PCT/JP2013/083826 JP2013083826W WO2014162641A1 WO 2014162641 A1 WO2014162641 A1 WO 2014162641A1 JP 2013083826 W JP2013083826 W JP 2013083826W WO 2014162641 A1 WO2014162641 A1 WO 2014162641A1
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Prior art keywords
dye
electrolyte
solar cell
basic substance
sensitized solar
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PCT/JP2013/083826
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English (en)
Japanese (ja)
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大介 松本
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株式会社フジクラ
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Priority claimed from JP2013075449A external-priority patent/JP5380618B1/ja
Priority claimed from JP2013075448A external-priority patent/JP5380617B1/ja
Application filed by 株式会社フジクラ filed Critical 株式会社フジクラ
Publication of WO2014162641A1 publication Critical patent/WO2014162641A1/fr

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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
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
    • 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
    • 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
    • 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 an electrolyte for a dye-sensitized solar cell and a dye-sensitized solar cell.
  • the dye-sensitized solar cell is a next-generation solar cell that has been developed by Gretzel et al. In Switzerland and has received attention because it has advantages such as high photoelectric conversion efficiency and low manufacturing cost.
  • a dye-sensitized solar cell generally includes a working electrode, a counter electrode, a photosensitizing dye supported on the oxide semiconductor layer of the working electrode, and an electrolyte disposed between the working electrode and the counter electrode.
  • the electrolyte contains a redox pair composed of, for example, halogen and halide ions.
  • Patent Document 1 discloses an electrolyte containing an ionic liquid, and according to this electrolyte, since the volatility of the electrolyte is reduced, the durability of the dye-sensitized solar cell can be improved. It is disclosed.
  • the dye-sensitized solar cell provided with the electrolyte described in Patent Document 1 still has room for improvement in photoelectric conversion characteristics. Therefore, when used as an electrolyte for a dye-sensitized solar cell, an electrolyte for a dye-sensitized solar cell that can further improve the photoelectric conversion characteristics of the dye-sensitized solar cell has been desired.
  • This invention is made
  • the present inventor conducted intensive studies focusing on the components of the electrolyte. As a result, the present inventors have found that the above-described problems can be solved by the following invention.
  • the present invention includes a halogen, a halide salt, a hydrogen halide, and at least one selected from the group consisting of a basic substance and a mixture of the basic substance and the salt of the hydrogen halide,
  • An oxidation-reduction pair is formed by the halogen and the halide salt, and the halogen, the halide salt, and the hydrogen halide have the same halogen atom, and the volume molarity C 1 of the halogen or the basic is molarity C 3 material, the molarity C 2 of the hydrogen halide, the basic substance and the total molarity C 20 larger dye with molarity C 4 salts of the hydrogen halide It is an electrolyte for a solar cell.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell can be sufficiently improved.
  • the electrolyte for a dye-sensitized solar cell includes the halogen, the halide salt, and the hydrogen halide, and the volume molar concentration C 1 of the halogen is the volume molar concentration C 2 of the hydrogen halide. greater than the total molarity C 20 with molarity C 4 salts of said basic material and the hydrogen halide, that molarity C 4 salts of said basic material and the hydrogen halide is 0mM Is preferred.
  • the dye-sensitized solar cell electrolyte includes a halogen, a halide salt, and a hydrogen halide, and the halogen and the halide salt form an oxidation-reduction pair, and the halogen, the halide salt, and It is preferable that the hydrogen halide has the same halogen atom, and the volume molar concentration C 1 of the halogen is larger than the volume molar concentration C 2 of the hydrogen halide.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell can be more sufficiently improved.
  • the present inventor presumes the reason why such an effect is obtained as follows. That is, when the electrolyte of the present invention is used as an electrolyte of a dye-sensitized solar cell having an oxide semiconductor layer made of an oxide semiconductor, hydrogen halide increases the level of the valence band of the oxide semiconductor layer. In addition, the electron injection efficiency between the dye and the oxide semiconductor can be improved. In addition, the HOMO (bonding orbital) level of the redox couple in the electrolyte is less likely to shift. In other words, it is possible to prevent the redox level from changing from an appropriate position due to hydrogen halide. For this reason, this inventor estimates that the photoelectric conversion characteristic of a dye-sensitized solar cell can fully be improved.
  • the volume molar concentration C 1 of the halogen is preferably twice or more the volume molar concentration C 2 of the hydrogen halide.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell can be particularly sufficiently improved.
  • the halogenated molarity C 2 hydrogens is preferably 0.05 ⁇ 15 mM.
  • the electrolyte is, when used as an electrolyte of a dye-sensitized solar cell including an oxide semiconductor layer formed of an oxide semiconductor, as compared with the case C 2 is less than 0.05 mM, hydrogen halide oxide
  • the level of the valence band of the semiconductor can be increased, and the electron injection efficiency between the dye and the oxide semiconductor can be further improved. Further, as compared with the case where C 2 is more than 15 mM, it can be more sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell.
  • the halogen atom is preferably an iodine atom.
  • the HOMO (bonding orbital) level of the photosensitizing dye used in the dye-sensitized solar cell and the level of the redox pair in the electrolyte are in an appropriate position, the electron injection efficiency can be further improved. it can.
  • the iodine reduction reaction is superior to other halogen species, the photosensitized photosensitizing dye can be instantaneously returned to the ground state, and the reverse reaction by the photosensitizing dye can be prevented.
  • the electrolyte for a dye-sensitized solar cell includes the halogen, the halide salt, the basic substance, and the salt of the basic substance and the hydrogen halide, and the volume molar concentration of the basic substance.
  • C 3 is larger than the total molar molar concentration C 20 of the molar molar concentration C 2 of the hydrogen halide and the molar molar concentration C 4 of the basic substance and the salt of the hydrogen halide, and the volume of the hydrogen halide.
  • molar concentration C 2 may be 0 mM.
  • the dye-sensitized solar cell electrolyte includes a halogen, a halide salt, a basic substance, and a salt of the basic substance and a hydrogen halide, and is oxidized and reduced by the halogen and the halide salt. pair is formed, the halogen, the halide salt and the hydrogen halide has the same halogen atom, molarity C 3 of the basic substance, a salt with the hydrogen halide and said basic substance it may be a dye-sensitized solar cell electrolyte greater than the molarity C 4.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell can be more sufficiently improved.
  • the present inventor presumes the reason why such an effect is obtained as follows. That is, when the electrolyte of the present invention is used as an electrolyte of a dye-sensitized solar cell having an oxide semiconductor layer made of an oxide semiconductor, a salt of a basic substance and a hydrogen halide is added to the oxide semiconductor layer.
  • the electron band level can be increased, and the electron injection efficiency between the dye and the oxide semiconductor can be improved.
  • the HOMO (bonding orbital) level of the redox couple in the electrolyte is less likely to shift. In other words, it is possible to prevent the redox level from changing from an appropriate position due to a salt of a basic substance and hydrogen halide. For this reason, this inventor estimates that the photoelectric conversion characteristic of a dye-sensitized solar cell can fully be improved.
  • molarity C 3 of the basic material is the basic material is three times or more molarity C 4 of the salt with the hydrogen halide.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell can be more sufficiently improved.
  • the molar concentration C 4 of the salt of the basic substance and the hydrogen halide is preferably 0.05 to 15 mM.
  • the electrolyte is, when used as an electrolyte of a dye-sensitized solar cell including an oxide semiconductor layer formed of an oxide semiconductor, as compared with the case C 4 is less than 0.05 mM, basic substance and halogenated
  • the salt with hydrogen can raise the level of the valence band of the oxide semiconductor, and the electron injection efficiency between the dye and the oxide semiconductor can be further improved. Further, as compared with the case where C 4 exceeds 15 mM, it is possible to more sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell.
  • the present invention also provides a first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate, a second electrode facing the first electrode, and an oxidation provided on the first electrode or the second electrode.
  • a dye-sensitized solar cell comprising: an organic semiconductor layer; an electrolyte provided between the first electrode and the second electrode; and a photosensitizing dye adsorbed on the oxide semiconductor layer. It is a dye-sensitized solar cell which is an electrolyte for use.
  • the electrolyte is the above-described dye-sensitized solar cell electrolyte, the photoelectric conversion characteristics can be sufficiently improved.
  • the present invention also provides an electrolyte for preparing an electrolytic solution containing a halogen, a halide salt, a salt of a basic substance and a hydrogen halide, wherein a redox pair is formed by the halogen and the halide salt.
  • the halogen and the halide salt and having said hydrogen halide is the same halogen atom, in the basic material mixing step, molarity C 3 of the basic substance, molarity of the salt with the hydrogen halide and said basic substance it is the electrolyte and a manufacturing method of the basic substance and mixing the dye-sensitized solar cell electrolyte to be greater than C 4.
  • an electrolyte for a dye-sensitized solar cell that can sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell can be produced.
  • the electrolytic solution and the basic substance are mixed so that the volume molar concentration C 3 of the basic substance is less than three times the volume molar concentration C 4 of the salt of the basic substance and hydrogen halide.
  • the obtained electrolyte can more sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell.
  • a salt with a basic substance and a hydrogen halide of the valence band of the oxide semiconductor The level can be increased and the electron injection efficiency between the dye and the oxide semiconductor can be further improved. Further, as compared with the case where C 4 exceeds 15 mM, electrolyte obtained can be more sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell.
  • the halogen atom is preferably an iodine atom.
  • the electrolyte when used as an electrolyte of a dye-sensitized solar cell, the HOMO (bonding orbital) level of the photosensitizing dye used in the dye-sensitized solar cell and the level of the redox pair in the electrolyte are Since the position is appropriate, the electron injection efficiency can be further improved. Moreover, since the reduction reaction of iodine is superior to other halogen species, when the electrolyte is used as an electrolyte of a dye-sensitized solar cell, the photosensitized photosensitizing dye can be instantaneously returned to the ground state, The reverse reaction by a photosensitizing dye etc. can be prevented.
  • the basic substance refers to a substance that can form a salt with hydrogen halide.
  • an electrolyte for a dye-sensitized solar cell and a dye-sensitized solar cell that can sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell are provided.
  • FIG. 1 is a cross-sectional view showing an embodiment of the dye-sensitized solar cell of the present invention.
  • the dye-sensitized solar cell 100 connects a working electrode 10 having a transparent conductive substrate 15, a counter electrode 20 facing the transparent conductive substrate 15, and the transparent conductive substrate 15 and the counter electrode 20.
  • the cell space formed by the transparent conductive substrate 15, the counter electrode 20 and the sealing portion 30 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 second electrode is constituted by the conductive substrate 21.
  • the working electrode 10 has a 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 oxide semiconductor layer 13 is disposed inside the sealing portion 30.
  • a photosensitizing dye is adsorbed on the oxide semiconductor layer 13.
  • the first electrode is constituted by the transparent conductive substrate 15.
  • the electrolyte 40 includes at least one selected from the group consisting of halogens, halide salts, hydrogen halides, and mixtures of basic substances, basic substances, and salts of hydrogen halides.
  • a redox pair is formed by the halogen and the halide salt.
  • the halogen, the halide salt and the hydrogen halide have the same halogen atom.
  • molarity C 1 of the halogen, the total molarity of the molarity C 2 hydrogen halide, the molarity C 4 salts of a basic substance and hydrogen halides C It is larger than 20 .
  • molarity C 4 salts of a basic substance and hydrogen halide is 0 mM. That is, molarity C 1 halogen is larger than the molarity C 2 hydrogen halide.
  • the electrolyte 40 since the electrolyte 40 has the above configuration, the photoelectric conversion characteristics can be sufficiently improved.
  • 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 100 and is not particularly limited, but may be in the range of 50 to 40,000 ⁇ m, for example.
  • the transparent conductive film 12 As a material constituting the transparent conductive film 12, for example, tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO). And conductive metal oxides such as 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, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, or 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 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 contains halogen, a halide salt, and hydrogen halide.
  • a redox pair is formed by the halogen and the halide salt.
  • the halogen, the halide salt and the hydrogen halide have the same halogen atom.
  • the volume molar concentration C 1 of the halogen is larger than the volume molar concentration C 2 of the hydrogen halide, that is, the value of C 1 / C 2 is larger than 1.
  • examples of the halogen atom constituting the halogen, halide salt and hydrogen halide include a bromine atom and an iodine atom.
  • the halogen atom constituting the halogen, halide salt and hydrogen halide is preferably an iodine atom. That is, it is preferable that the halogen is iodine, the halide salt is an iodide salt, and the hydrogen halide is hydrogen iodide.
  • the HOMO (bonding orbital) level of the photosensitizing dye used in the dye-sensitized solar cell 100 and the redox level in the electrolyte are in proper positions, the electron injection efficiency is further improved.
  • the iodine reduction reaction is superior to other halogen species, the photosensitized photosensitizing dye can be instantaneously returned to the ground state, and the reverse reaction by the photosensitizing dye can be prevented.
  • halide salt contained in the electrolyte 40 examples include lithium bromide, sodium bromide, potassium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetrahexylammonium bromide, 1-hexyl-3- Bromide salts such as methyl imidazolium bromide, 1-ethyl-3-propyl imidazolium bromide, dimethyl imidazolium bromide, ethyl methyl imidazolium bromide, dimethylpropyl imidazolium bromide, butyl methyl imidazolium bromide, methyl propyl imidazolium bromide, iodine Lithium iodide, sodium iodide, potassium iodide, tetramethylammonium iodide, tetraethylammonium i
  • examples of the hydrogen halide contained in the electrolyte 40 include hydrogen bromide and hydrogen iodide.
  • Examples of the redox pair formed by halogen and a halide salt include combinations of halide ions and polyhalide ions. Specific examples include I ⁇ / I 3 — and Br ⁇ / Br 3 — .
  • molarity C 1 halogen twice more molarity C 2 hydrogen halide that is, the value of C 1 / C 2 is preferably by 2 or more.
  • C 1 / C 2 is more preferably 2.5 to 300, and further preferably 10 to 250.
  • Molarity C 1 halogen as described above, may be greater than the volume molar concentration C 2 of the hydrogen halide.
  • the volume molar concentration C 2 of hydrogen halide is preferably 0.05 to 15 mM.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell 100 can be more sufficiently improved than when C 2 exceeds 15 mM. Can do. Further, when the volume molar concentration C 2 of hydrogen halide is in the range of 0.05 to 15 mM, the hydrogen halide is in the valence band of the oxide semiconductor as compared with the case where C 2 is less than 0.05 mM. The level can be increased and the electron injection efficiency between the dye and the oxide semiconductor can be further improved.
  • C 2 is more preferably 0.06 to 14 mM, and further preferably 0.07 to 13 mM.
  • Electrolyte 40 may further contain 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. These may be used alone or in combination of two or more.
  • the electrolyte 40 may further contain an additive.
  • the additive include 4-t-butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, and 1-butylbenzimidazole.
  • 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 examples include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine.
  • a ruthenium complex having a ligand containing a terpyridine structure is preferable. In this case, the photoelectric conversion characteristics of the dye-sensitized solar cell 100 can be further improved.
  • a ruthenium complex having a ligand containing a bipyridine structure may be used as the photosensitizing dye. preferable.
  • 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 (SPD), 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.
  • a photosensitizing dye 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.
  • the photosensitizing dye may be adsorbed to the oxide semiconductor layer 13 by applying a solution containing the photosensitizing dye to the oxide semiconductor layer 13 and then drying the solution.
  • the electrolyte 40 contains the halogen, halide salt, and hydrogen halide described above, and is obtained by adjusting the C 1 / C 2 value to be greater than 1. At this time, in the electrolyte 40, a redox pair is formed by the halogen and the halide salt.
  • 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 100 is obtained as described above.
  • FIG. 2 is a cross-sectional view showing a second embodiment of the dye-sensitized solar cell of the present invention.
  • the dye-sensitized solar cell 200 of the present embodiment is different from the dye-sensitized solar cell 100 of the first embodiment in that an electrolyte 240 is used instead of the electrolyte 40.
  • the electrolyte 240 includes a halogen, a halide salt, a basic substance, and a salt of the basic substance and hydrogen halide.
  • a redox pair is formed by halogen and a halide salt.
  • the halogen, the halide salt and the hydrogen halide have the same halogen atom.
  • the total molarity of molarity C 3 of the basic substance, the molarity C 2 hydrogen halide, the molarity C 4 salts of a basic substance and a hydrogen halide It is greater than C 20.
  • molarity C 2 hydrogen halide is in the 0 mM. That is, molarity C 3 of the basic substance is greater than the molarity C 4 of the salt with the basic substance and the hydrogen halide. That is, the value of C 3 / C 4 is larger than 1.
  • examples of the halogen atom contained in the halogen, halide salt, and hydrogen halide include a bromine atom and an iodine atom.
  • the halogen atom which a halogen, a halide salt, and a hydrogen halide have is an iodine atom. That is, it is preferable that the halogen is iodine, the halide salt is an iodide salt, and the hydrogen halide is hydrogen iodide.
  • the electrolyte 240 can instantaneously return the photosensitized photosensitizing dye to the ground state, and hinder the reverse reaction by the photosensitizing dye. it can.
  • the basic substance examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylamine, tetraethylamine, tetrabutylamine, tetrahexylamine, 1-hexyl-3-methylimidazole, and 1-ethyl.
  • -3-Propylimidazole, dimethylimidazole, ethylmethylimidazole, dimethylpropylimidazole, butylmethylimidazole, methylpropylimidazole, methylbenzimidazole, butylbenzimidazole, t-butylpyridine, guanidinium thiocyanate and the like are preferably used.
  • a basic substance may be used individually by 1 type, or may be used in combination of 2 or more types.
  • molarity C 3 of the basic substance is a basic substance and more than three times the molarity C 4 of the salts with hydrogen halides, i.e. the value of C 3 / C 4 is 3 or more It is preferable.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell 200 can be particularly sufficiently improved.
  • the C 3 / C 4 value is more preferably 3 to 1000, and even more preferably 7 to 900.
  • the volume molar concentration C 3 of the basic substance may be larger than the volume molar concentration C 4 of the salt of the basic substance and hydrogen halide as described above.
  • volume molar concentration C 4 of the salt of the basic substance and the hydrogen halide is preferably 0.05 to 15 mM.
  • the electrolyte 4 can sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell 200 as compared with the case where C 4 exceeds 15 mM.
  • the salt of the basic substance and the hydrogen halide is in the valence band of the oxide semiconductor as compared to the case where C 4 is less than 0.05 mM. The level can be increased and the electron injection efficiency between the dye and the oxide semiconductor can be further improved.
  • C 4 is more preferably 0.06 to 14 mM, and further preferably 0.07 to 13 mM.
  • the method for manufacturing the dye-sensitized solar cell 200 is different from the method for manufacturing the dye-sensitized solar cell 100 in that the electrolyte 240 is used instead of the electrolyte 40.
  • the electrolyte 240 includes a halogen, a halide salt, a salt of a basic substance and a hydrogen halide, and an electrolyte solution preparing step of preparing an electrolyte solution in which a redox pair is formed by the halogen and the halide salt. And a basic substance mixing step of mixing the electrolytic solution and the basic substance to obtain the electrolyte 240. At this time, in the electrolytic solution preparation step, the halogen, halide salt, and hydrogen halide have the same halogen atom. In the basic substance mixing step, the electrolytic solution and the basic substance are mixed so that the volume molar concentration C 3 of the basic substance is larger than the volume molar concentration C 4 of the salt of the basic substance and hydrogen halide. Mix.
  • a halogen and a halide salt are dissolved in the organic solvent described above to prepare a solution containing a redox pair formed by the halogen and the halide salt.
  • the electrolyte 240 is obtained. According to the manufacturing method of the electrolyte 240 described above, the obtained electrolyte 240 can sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell 200.
  • the photoelectric conversion characteristics of the dye-sensitized solar cell 200 can be more sufficiently improved by the electrolyte 240 thus obtained.
  • the electrolytic solution and the basic substance so that the value of C 3 / C 4 is 3 to 1000, and the electrolytic solution and the basic substance are mixed so as to be 7 to 900. More preferably.
  • molarity C 4 of salt with a basic substance and hydrogen halide is mixed with the electrolytic solution and the basic substance so that 0.05 ⁇ 15 mM.
  • the electrolyte 240 can sufficiently improve the photoelectric conversion characteristics of the dye-sensitized solar cell 200 as compared with the case where C 4 exceeds 15 mM.
  • the salt of the basic substance and the hydrogen halide is in the valence band of the oxide semiconductor as compared to the case where C 4 is less than 0.05 mM. The level can be increased and the electron injection efficiency between the dye and the oxide semiconductor can be further improved.
  • the present invention is not limited to the above embodiment.
  • the porous oxide semiconductor layer 13 is provided on the transparent conductive substrate 15 to receive light from this side, but the base material on which the porous oxide semiconductor layer 13 is formed is provided.
  • An opaque material for example, a metal substrate
  • a transparent material may be used for the base material on which the counter electrode 20 is formed
  • a structure for receiving light from the counter electrode side may be used.
  • molarity C 1 of iodine in the electrolyte is 30 mM
  • molarity C 1 iodine by ultraviolet-visible (UV-vis) absorption spectroscopy using a spectrophotometer
  • molarity of hydrogen iodide was determined by neutralization titration with potassium hydroxide.
  • the salt molar concentration C 4 was 0 mM as described in Table 1.
  • an electrolyte for a dye-sensitized solar cell was prepared. In this electrolyte, an oxidation-reduction pair was formed by iodine and hydrogen iodide.
  • an FTO / glass substrate having an FTO film formed on a glass substrate was prepared. Then, this FTO / glass substrate is cleaned, this substrate is subjected to UV-O 3 treatment, and a titanium oxide nanoparticle paste containing titanium oxide is applied onto the substrate by screen printing to produce a 50 ⁇ 50 mm film. And dried at 150 ° C. for 10 minutes. Thus, an unfired substrate was obtained. Thereafter, this unfired substrate was put in an oven, and the titanium oxide nanoparticle paste was fired at 500 ° C. for 1 hour to form a porous titanium oxide layer having a thickness of 14 ⁇ m on the FTO film, thereby obtaining a working electrode.
  • the photosensitizing dye Z907 dye was dissolved in a mixed solvent of acetonitrile and t-butyl alcohol mixed at 1: 1 (volume ratio) to prepare a dye solution. Then, the working electrode was immersed in this dye solution for 24 hours, and the photosensitizing dye was supported on the porous titanium oxide layer.
  • the FTO / glass substrate used in the production of the working electrode was prepared, and Pt was deposited on this substrate by a sputtering method. In this way, a counter electrode was obtained.
  • an annular thermoplastic resin sheet made of ionomer Himiran (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was placed on the working electrode.
  • the porous titanium oxide layer was arranged inside the annular thermoplastic resin sheet.
  • the thermoplastic resin sheet was heated and melted at 180 ° C. for 5 minutes to adhere to the working electrode.
  • the electrolyte prepared as described above was applied by screen printing so as to cover the porous titanium oxide layer on the working electrode.
  • the counter electrode was superposed on the working electrode so that the electrolyte was sandwiched between the working electrode and the sealed portion was heated and melted under reduced pressure (1000 Pa) to adhere the counter electrode and the sealed portion.
  • NMBIm methylbenzimidazole
  • NBP butylbenzimidazole
  • TBP t-butylpyridine
  • GNSCN guani Represents thiocyanate.
  • the volume molar concentration C 4 in the electrolyte is adjusted to the volume molar concentration described as “salt concentration C 4 ” in Tables 2 to 6 in the above mixture. Dissolved.
  • the volume molar concentration C 4 of the salt of the basic substance and hydrogen iodide was quantified by a quantitative titration method. In the obtained electrolyte, an oxidation-reduction pair was formed by iodine and hydrogen iodide.
  • the molarity C 3 of the basic substance in the electrolyte was set to 100 mM.
  • Examples 20 to 24 and Comparative Examples 16 to 18 shown in Table 6 were prepared so that the NMBIm had a molar molar concentration of 50 mM and the GuSCN had a molar molar concentration of 50 mM.
  • Molarity C 3 of the basic substance was quantified by quantitative titration.
  • the volume molar concentration C 2 of the hydrogen iodide in the electrolyte was 0 mM.
  • the volume molar concentration of hydrogen iodide was determined by neutralization titration with potassium hydroxide.
  • an FTO / glass substrate having an FTO film formed on a glass substrate was prepared. Then, this FTO / glass substrate is cleaned, this substrate is subjected to UV-O 3 treatment, and a titanium oxide nanoparticle paste containing titanium oxide is applied onto the substrate by screen printing to produce a 50 ⁇ 50 mm film. And dried at 150 ° C. for 10 minutes. Thus, an unfired substrate was obtained. Thereafter, this unfired substrate was put in an oven, and the titanium oxide nanoparticle paste was fired at 500 ° C. for 1 hour to form a porous titanium oxide layer having a thickness of 14 ⁇ m on the FTO film, thereby obtaining a working electrode.
  • the photosensitizing dye Z907 dye was dissolved in a mixed solvent of acetonitrile and t-butyl alcohol mixed at 1: 1 (volume ratio) to prepare a dye solution. Then, the working electrode was immersed in this dye solution for 24 hours, and the photosensitizing dye was supported on the porous titanium oxide layer.
  • the FTO / glass substrate used in the production of the working electrode was prepared, and Pt was deposited on this substrate by a sputtering method. In this way, a counter electrode was obtained.
  • an annular thermoplastic resin sheet made of ionomer Himiran (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was placed on the working electrode.
  • the porous titanium oxide layer was arranged inside the annular thermoplastic resin sheet.
  • the thermoplastic resin sheet was heated and melted at 180 ° C. for 5 minutes to adhere to the working electrode.
  • the electrolyte prepared as described above was applied by screen printing so as to cover the porous titanium oxide layer on the working electrode.
  • the counter electrode was superposed on the working electrode so that the electrolyte was sandwiched between the working electrode and the sealed portion was heated and melted under reduced pressure (1000 Pa) to adhere the counter electrode and the sealed portion.
  • the photoelectric conversion efficiency ⁇ (%) of the dye-sensitized solar cells of Examples 5 to 24 and Comparative Examples 4 to 18 obtained as described above was measured.
  • Comparative Example 4 was used as a reference comparative example, and Examples 9 to 12 and Comparative Examples 7 to 7 using NBB as a basic substance were used.
  • Comparative Example 7 was used as a standard comparative example, and Examples 13 to 16 and Comparative Examples 10 to 12 using TBP as a basic substance were used as Comparative Examples 10 and GuSCN was used as a basic substance.
  • Comparative Example 13 was used as a reference comparative example, and for Examples 21 to 24 and Comparative Examples 16 to 18 using NMBIm and GuSCN as basic substances, Comparative Example 16 was used as a reference comparison.
  • the rate of increase in photoelectric conversion efficiency ⁇ was calculated based on the following formula. The results are shown in Tables 2-6.
  • Rate of increase in photoelectric conversion efficiency 100 ⁇ (photoelectric conversion efficiency of example or comparative example ⁇ photoelectric conversion efficiency of comparative example 1) / photoelectric conversion efficiency of comparative example 1
  • the photoelectric conversion efficiency was measured using a Xe lamp solar simulator (YSS-150, Yamashita Denso Co., Ltd.) and an IV tester (MP-160, Eiko Seiki Co., Ltd.).

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Abstract

L'invention concerne un électrolyte pour une cellule solaire sensibilisée par colorant, ledit électrolyte contenant un halogène, un sel d'halogénure et au moins un élément choisi parmi le groupe composé de : un halogénure d'hydrogène ; et un mélange d'une substance de base, un sel de la substance de base et de l'halogénure d'hydrogène. Un couple redox est formé par l'halogène et le sel d'halogénure. L'halogène, le sel d'halogénure et l'halogénure d'hydrogène possèdent le même atome d'halogène. La concentration molaire volumique (C1) de l'halogène, ou la concentration molaire volumique (C3) de la substance de base est supérieure à la concentration molaire volumique totale (C20) de la concentration molaire volumique (C2) de l'halogénure d'hydrogène et la concentration molaire volumique (C4) du sel de la substance de base et de l'halogénure d'hydrogène.
PCT/JP2013/083826 2013-03-30 2013-12-18 Électrolyte pour cellule solaire sensibilisée par colorant et cellule solaire sensibilisée par colorant WO2014162641A1 (fr)

Applications Claiming Priority (4)

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JP2013075449A JP5380618B1 (ja) 2013-03-30 2013-03-30 色素増感太陽電池用電解質、その製造方法、及び、色素増感太陽電池
JP2013-075448 2013-03-30
JP2013075448A JP5380617B1 (ja) 2013-03-30 2013-03-30 色素増感太陽電池用電解質および色素増感太陽電池
JP2013-075449 2013-03-30

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012104427A (ja) * 2010-11-12 2012-05-31 Everlight Usa Inc 電解質組成物及びそれを用いた色素増感太陽電池

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012104427A (ja) * 2010-11-12 2012-05-31 Everlight Usa Inc 電解質組成物及びそれを用いた色素増感太陽電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN ET AL.: "On the use of triethylamine hydroiodide as a supporting electrolyte in dye- sensitized solar cells", SOLAR ENERGY MATERIALS & SOLAR CELLS, vol. 91, no. 15-16, 2007, pages 1432 - 1437 *

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