JP2016143867A - Dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell having excellent short-circuit current density and photoelectric conversion efficiency.SOLUTION: The dye-sensitized solar cell includes: a dye which is a non-metal complex organic dye; and a charge transfer layer containing iodine, iodine ions, and a compound represented by the formula below. (Rto Rare O, N, S, halogen, or H that may have a covalent bond with a substituent group selected from an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue of C1 to 10 that may have a substituent group such as alkoxy, amide, alkyl, nitro, and a H atom.SELECTED DRAWING: None

Description

  The present invention relates to a dye-sensitized solar cell capable of realizing an excellent short-circuit current density and photoelectric conversion efficiency.

  In recent years, solar cells, which are attracting attention as a clean energy source, have come to be used in ordinary houses. However, it has not yet reached widespread use. One of the reasons is that it is difficult to say that the performance of the solar cell itself is sufficiently excellent, and the module must be enlarged. Another reason is that the solar cell itself is expensive because the productivity in module manufacturing is low.

  There are several types of solar cells, but most of the solar cells in practical use are silicon solar cells. However, recently, a dye-sensitized solar cell has been attracting attention and has been studied for its practical use. The prototype of the present dye-sensitized solar cell was developed by Gretzell (Switzerland) et al. In 1991 and is also called Gretzell cell. Its structure consists of a conductive support (oxide semiconductor electrode) having an oxide semiconductor fine particle layer sensitized by a dye serving as one pole, and a conductive support having a counter electrode arranged with platinum or the like so as to face it. It is generally composed of a body (counter electrode), a charge transfer layer (electrolyte containing a redox substance, etc.) sandwiched between both electrodes, and a sealing agent such as a resin disposed around the charge transfer layer. . Moreover, the performance of a dye-sensitized solar cell has reached the photoelectric conversion efficiency equivalent to an amorphous silicon solar cell by adsorb | sucking a ruthenium complex pigment | dye to a porous titanium oxide electrode, for example (nonpatent literature 1). However, many problems still remain for its practical application. In order to enable the practical use of a dye-sensitized solar cell as an alternative to the high cost silicon solar cell, further improvement in photoelectric conversion efficiency of the dye-sensitized solar cell is desired.

Sensitizing dyes that influence the photoelectric conversion efficiency of dye-sensitized solar cells are roughly classified into two systems, metal complex dyes and nonmetal complex dyes. In recent years, non-metallic complex dyes with few resource constraints and a wide range of molecular designs have been actively developed (Non-patent Document 2). In addition, an electrolyte solution containing an iodine-based redox pair having a well-balanced performance is generally used for a charge transfer layer related to both photoelectric conversion efficiency and durability of a dye-sensitized solar cell. In order to improve the performance of dye-sensitized solar cells, studies have been made to add additives to this electrolyte solution. For example, a technique of adding a nitrogen-containing compound typified by 4-tert-butylpyridine to an electrolyte in order to improve the open-circuit voltage, which is one of the factors that determine photoelectric conversion efficiency, is widely known ( Non-patent document 2). However, since these nitrogen-containing compounds are highly basic, if a nonmetal complex dye is added to the electrolyte of a dye-sensitized solar cell using the sensitizing dye, the durability is greatly reduced. In addition, a dye-sensitized solar cell using a metal complex dye as a sensitizing dye, and a dye-sensitized solar cell in which a compound of the same type as the ligand of the metal complex is added to the electrolyte have been reported. However, these effects cannot be obtained in a dye-sensitized solar cell using a non-metal complex dye as a sensitizing dye (Patent Document 1). In addition, a new redox system composed of iodine, pyridine and acetylacetone has been proposed. However, since pyridine has basicity, in a dye-sensitized solar cell using a nonmetal complex dye as a sensitizing dye as described above, It is difficult to apply (Non Patent Literature 3).
As described above, although dye-sensitized solar cells having electrolytes containing non-metal complex dyes and iodine-based redox as constituent members are highly expected for their practical use, in order to improve their performance At present, effective electrolyte additives are still limited.

Japanese Patent No. 4210054

Nature, 353, 737-740, 1991. Chemical Reviews, Vol. 110, No. 11, pp. 6595-6663, 2010 Electrochemistry Communications, Vol. 9, 1735-1738, 2007

  An object of the present invention is to provide a dye-sensitized solar cell using a non-metal complex dye that can realize an excellent short-circuit current density and photoelectric conversion efficiency.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a nonmetallic complex dye as a sensitizing dye, and iodine, iodine ion and a compound represented by formula (1) in a charge transfer layer. It has been found that a dye-sensitized solar cell using an electrolyte solution containing is excellent in short-circuit current density and photoelectric conversion efficiency.

That is, the present invention
(1) a first conductive support having a semiconductor-containing layer sensitized by a dye, and a second conductive having a counter electrode provided at a position where the semiconductor-containing layer and the counter electrode face each other at a predetermined interval A conductive support, a charge transfer layer sandwiched between the first and second conductive supports, and a peripheral portion of the first and second conductive supports for sealing the charge transfer layer. A dye-sensitized solar cell including a sealant, wherein the dye is a non-metallic complex organic dye, and the charge transfer layer contains iodine, iodine ions, and a compound represented by the following formula (1) A dye-sensitized solar cell that is an electrolyte solution,

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に、ハロゲン原子、アルコキシ基、エステル基、アシル基、アミノ基、アミド基、アルキル基、アルケニル基、アルキニル基、アリール基、シアノ基、イソシアノ基、ニトロ基、ニトロソ基、ヒドロキシル基、リン酸エステル基、スルフィニル基及びスルホニル基からなる群より選ばれる一種以上の置換基を有していてもよい炭素数１〜１０の脂肪族炭化水素残基、ハロゲン原子、アルコキシ基、エステル基、アシル基、アミノ基、アミド基、アルキル基、アルケニル基、アルキニル基、アリール基、シアノ基、イソシアノ基、ニトロ基、ニトロソ基、ヒドロキシル基、リン酸エステル基、スルフィニル基及びスルホニル基からなる群より選ばれる一種以上の置換基を有していてもよい芳香族炭化水素残基、ハロゲン原子、アルコキシ基、エステル基、アシル基、アミノ基、アミド基、アルキル基、アルケニル基、アルキニル基、アリール基、シアノ基、イソシアノ基、ニトロ基、ニトロソ基、ヒドロキシル基、リン酸エステル基、スルフィニル基及びスルホニル基からなる群より選ばれる一種以上の置換基を有していてもよい複素環残基、前記脂肪族炭化水素残基、芳香族炭化水素残基、複素環残基及び水素原子からなる群より選ばれる一種以上の置換基と共有結合を有していてもよい酸素原子、前記脂肪族炭化水素残基、芳香族炭化水素残基、複素環残基及び水素原子からなる群より選ばれる一種以上の置換基と共有結合を有していてもよい窒素原子、前記脂肪族炭化水素残基、芳香族炭化水素残基、複素環残基及び水素原子からなる群より選ばれる一種以上の置換基と共有結合を有していてもよい硫黄原子、ハロゲン原子若しくは水素原子を表す。また、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４から選択される任意の２者で結合して環を形成してもよい。）
（２）式（１）で表される化合物がβジケトン、βケトエステル及びβケトアミドからなる群から選ばれる一種又は二種以上である前項（１）に記載の色素増感太陽電池、
（３）式（１）で表される化合物の電荷移動層中の含有量が０．０１〜５Ｍである前項（１）又は（２）に記載の色素増感太陽電池、
（４）含硫化合物を電荷移動層中に含有する前項（１）乃至（３）の何れか一項に記載の色素増感太陽電池、
（５）電荷移動層中に含有する含硫化合物が、チオシアネート、チオエステル結合を有する化合物のいずれかである前項（４）に記載の色素増感太陽電池、
（６）シール剤が、エポキシ樹脂系シール剤である前項（１）乃至（５）のいずれか一項に記載の色素増感太陽電池、
（７）半導体含有層の半導体が、微粒子状の酸化チタン又は微粒子状の複合酸化チタンである前項（１）乃至（６）のいずれか一項に記載の色素増感太陽電池、
（８）非金属錯体系の有機色素が、下記式（２）

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group or aryl group , A cyano group, an isocyano group, a nitro group, a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group, which may have one or more substituents selected from the group consisting of 1 to 10 carbon atoms Aliphatic hydrocarbon residue, halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, nitroso group, hydroxyl It may have one or more substituents selected from the group consisting of a group, a phosphate ester group, a sulfinyl group and a sulfonyl group. Aromatic hydrocarbon residue, halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, nitroso group, hydroxyl A heterocyclic residue which may have one or more substituents selected from the group consisting of a group, a phosphate ester group, a sulfinyl group and a sulfonyl group, the aliphatic hydrocarbon residue, the aromatic hydrocarbon residue, An oxygen atom which may have a covalent bond with one or more substituents selected from the group consisting of a heterocyclic residue and a hydrogen atom, the aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue And a nitrogen atom which may have a covalent bond with one or more substituents selected from the group consisting of hydrogen atoms, the aliphatic hydrocarbon residues, aromatic hydrocarbon residues, heterocyclic residues and water One or more substituents covalently bonded may have a sulfur atom selected from the group consisting of atoms, a halogen atom or a hydrogen atom. In addition, selected from R _{1, R 2,} R ₃ and R ₄ Any two of them may combine to form a ring.)
(2) The dye-sensitized solar cell according to item (1), wherein the compound represented by the formula (1) is one or more selected from the group consisting of β-diketone, β-ketoester, and β-ketoamide,
(3) The dye-sensitized solar cell according to (1) or (2), wherein the content of the compound represented by formula (1) in the charge transfer layer is 0.01 to 5M,
(4) The dye-sensitized solar cell according to any one of (1) to (3), wherein the sulfur-containing compound is contained in the charge transfer layer,
(5) The dye-sensitized solar cell according to (4), wherein the sulfur-containing compound contained in the charge transfer layer is any one of thiocyanate and a compound having a thioester bond,
(6) The dye-sensitized solar cell according to any one of (1) to (5), wherein the sealant is an epoxy resin sealant;
(7) The dye-sensitized solar cell according to any one of (1) to (6), wherein the semiconductor of the semiconductor-containing layer is particulate titanium oxide or particulate composite titanium oxide.
(8) A non-metallic complex organic dye is represented by the following formula (2)

（式中、Ａ_１及びＡ_２はそれぞれ独立にカルボキシル基、シアノ基、アルコキシカルボニル基、アシル基、ニトロ基、環式炭化水素残基、複素環残基、アミノ基、ヒドロキシル基、水素原子、ハロゲン原子又はアルキル基を表す。Ｘは芳香族炭化水素残基、複素環残基又はアミノ基を表す。ｎは１〜６の整数を表す。また、ｎが２以上で、Ａ_１及びＡ_２が複数存在する場合、それぞれのＡ_１及びそれぞれのＡ_２は互いに独立に同じ又は異なってもよい前記の基を表す。また、Ａ_１若しくはＡ_１が複数存在する場合にはそれぞれのＡ_１、Ａ_２若しくはＡ_２が複数存在する場合にはそれぞれのＡ_２及びＸの中の２者は結合して環を形成してもよい。）
で表される構造を有する（１）乃至（７）のいずれか一項に記載の色素増感太陽電池、
（９）式（２）におけるＡ_１が、シアノ基又はカルボキシル基である前項（８）に記載の色素増感太陽電池、
（１０）式（２）におけるＸが、トリフェニルアミン誘導体を有する（ポリ）エテニル基又は（ポリ）チオフェニル基である前項（８）又は（９）に記載の色素増感太陽電池、
に関する。

(In the formula, A ₁ and A ₂ are each independently a carboxyl group, a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyclic hydrocarbon residue, a heterocyclic residue, an amino group, a hydroxyl group, a hydrogen atom, Represents a halogen atom or an alkyl group, X represents an aromatic hydrocarbon residue, a heterocyclic residue or an amino group, n represents an integer of 1 to 6, and n is 2 or more, and A ₁ and A ₂ When a plurality of A _{1 s} are present, each A ₁ and each A ₂ each independently represent the same or different group, and when a plurality of A ₁ or A ₁ are present, each A ₁ , When _two or more of A ₂ or A ₂ are present, _two of each A ₂ and X may combine to form a ring.)
The dye-sensitized solar cell according to any one of (1) to (7), which has a structure represented by:
(9) The dye-sensitized solar cell according to (8), wherein A ₁ in formula (2) is a cyano group or a carboxyl group,
(10) The dye-sensitized solar cell according to item (8) or (9), wherein X in formula (2) is a (poly) ethenyl group or (poly) thiophenyl group having a triphenylamine derivative;
About.

  The dye-sensitized solar cell of the present invention is a dye-sensitized solar cell using a non-metallic complex-based organic dye with less resource constraints and a wide molecular design range, and can obtain a high short-circuit current density. Have excellent photoelectric conversion efficiency.

Cross-sectional schematic diagram of relevant parts for explaining the structure of the dye-sensitized solar cell of the present invention

The present invention is described in detail below.
The dye-sensitized solar cell of the present invention includes a first conductive support having a semiconductor-containing layer sensitized with a dye, and a counter provided at a position where the semiconductor-containing layer and the counter electrode face each other at a predetermined interval. Second conductive support having electrodes, charge transfer layer sandwiched between gaps of first and second conductive support, and first and second conductive supports for sealing charge transfer layer A dye-sensitized solar cell including a sealing agent provided in the periphery of the organic dye, wherein the dye is a non-metallic complex organic dye, and the charge transfer layer further comprises iodine, iodine ion, and formula (1) It is electrolyte solution containing the compound containing the compound represented.

The dye-sensitized solar cell of the present invention has a first conductive support having a semiconductor-containing layer sensitized with a dye.
Examples of the conductive support include conductive materials typified by FTO (fluorine-doped tin oxide), ATO (antimony-doped tin oxide), and ITO (indium-doped tin oxide), glass, plastic, polymer film, quartz, silicon, and the like. A thin film on the surface of the substrate is used. The thickness of the substrate is usually 0.01 to 10 mm, and the shape can take various forms from a film shape to a plate shape, but at least one of the first and second conductive supports has a light transmission property. A compatible substrate is used. The resistance value of the conductive support is usually 1000Ω / cm ² or less, preferably 100Ω / cm ² or less.

The oxide semiconductor used for the preparation of the semiconductor-containing layer is preferably metal chalcogenide fine particles, and specific examples thereof include transition metals such as Ti, Zn, Sn, Nb, W, In, Zr, Y, La, and Ta. Examples thereof include oxides, Al oxides, Si oxides, and perovskite oxides such as StTiO ₃ , CaTiO ₃ , and BaTiO ₃ . Of these, TiO ₂ , ZnO, and SnO ₂ are particularly preferable. These may be used as a mixture, and a preferred example is a SnO ₂ —ZnO mixed system. In the case of a mixed system, they may be mixed in the form of fine particles, mixed in a slurry or paste state described below, or the components may be used in layers. The primary particle size of the oxide semiconductor used here is usually 1 to 200 nm, preferably 1 to 50 nm. Further, for the purpose of improving the open circuit voltage and conversion efficiency of the dye-sensitized solar cell, as an oxide semiconductor, for example, titanium and magnesium, calcium, zirconium, strontium, etc. described in International Publication No. WO2006 / 080384 are disclosed. A composite oxide semiconductor manufactured by mixing non-titanium metal or the like can also be used.

  The sensitizing dye used in the dye-sensitized solar cell of the present invention is not particularly limited as long as it is a non-metallic complex organic dye having an action of sensitizing light absorption in combination with semiconductor fine particles constituting the semiconductor-containing layer, A single dye may be used, or several kinds of dyes may be mixed and used in an arbitrary ratio. When mixed and used, a wide absorption wavelength can be used by mixing dyes having different absorption wavelength regions, so that a solar cell with high conversion efficiency can be obtained.

  Specific examples of non-metallic complex organic dyes include cyanine-based, merocyanine-based, oxonol-based, triphenylmethane-based, acrylic acid-based dyes described in International Publication No. WO2002 / 011213, and International Publication No. WO2006 / 126538. Methine dyes such as pyrazolone methine dyes described in the publication, xanthene, azo, anthraquinone, perylene, indigo, acridine, indigo, quinone, coumarin, phenylxanthene, and central metals Examples thereof include phthalocyanine-based pigments that do not have, and porphyrin-based pigments that do not have a central metal. Among these, Japanese Patent No. 3731852, Japanese Patent Application Laid-Open No. 2002-334729, Japanese Patent Application Laid-Open No. 2002-512729, Japanese Patent Application Laid-Open No. 2003-007358, Japanese Patent Application Laid-Open No. 2003-171146, Japanese Patent Application Laid-Open No. 2003-059547. JP, 2003-086257, JP 2003-115333, JP 2003-132965, JP 2003-142172, JP 2003-151649, JP 2003-157915, JP 2003-282165 A, JP 2004-014175 A, JP 2004-022222 A, JP 2004-022387 A, JP 2004-227825 A, JP 2005-005026 A, JP 2005-019130, JP 2 No. 05-135656, JP-A-2006-079898, JP-A-2006-134649, JP-A-2007-149570, JP-A-2008-021496, JP-A-2010-146864, International Patent Publication WO2002 No./001667, International Publication No. WO2002 / 011213, International Publication No. WO2002 / 071530, International Publication No. WO2004 / 082061, International Publication No. WO2006 / 082061, International Publication No. WO2006 / 126538, The dyes described in International Patent Publication WO2007 / 100033, International Publication Patent WO2009 / 020098, International Publication WO2010 / 021378, etc. are preferred. And more preferably a methine dye or the like of acrylic acid or the like.

  Among these sensitizing dyes, the dye represented by the following formula (2) is particularly preferably used in the dye-sensitized solar cell of the present invention.

  In the present invention, the dye represented by the formula (2) is used in a meaning including both the free acid represented by the formula (2) and a salt thereof unless otherwise specified. Examples of the salt of the dye represented by the formula (2) include a metal salt in which the carboxylic acid moiety in the formula (2) is an alkali metal or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium. Or a compound that is a quaternary ammonium salt with tetramethylammonium, tetrabutylammonium, pyridinium, imidazolium, or the like.

In formula (2), A ₁ and A ₂ are each independently a carboxyl group, cyano group, alkoxycarbonyl group, acyl group, nitro group, cyclic hydrocarbon residue, heterocyclic residue, amino group, hydroxyl group, hydrogen An atom, a halogen atom or an alkyl group is represented. When a plurality of A ₁ and A ₂ are present, each A ₁ and each A ₂ each independently represent the same group as described above, which may be the same or different.
Examples of the alkyl group included in the alkoxycarbonyl group represented by A ₁ and A ₂ in Formula (2) include a saturated or unsaturated linear, branched or cyclic alkyl group which may have a substituent. The linear or branched alkyl group is preferably a C1-C36 alkyl group, more preferably a saturated C1-C20 linear alkyl group. As a cyclic thing, C3-C8 cycloalkyl etc. are mentioned, for example.
Examples of the acyl group represented by A ₁ and A ₂ in Formula (2) include C1-C10 alkylcarbonyl groups, arylcarbonyl groups, etc., preferably C1-C4 alkylcarbonyl groups, specifically acetyl groups, A propionyl group etc. are mentioned.

The cyclic hydrocarbon residue represented by A ₁ and A ₂ in the formula (2) means a group obtained by removing one hydrogen atom from a cyclic hydrocarbon, and examples of the cyclic hydrocarbon include a benzene ring, Naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, indene ring, azulene ring, fluorene ring, cyclohexane ring, cyclopentane ring, cyclohexene ring, cyclopentene ring, cyclohexadiene ring, cyclopentadiene ring and the like can be mentioned.
The cyclic hydrocarbon residue represented by A ₁ and A ₂ may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanato group, a nitro group. Group, nitrosyl group, acyl group, halogen atom, hydroxyl group, phosphate group, phosphate ester group, substituted or unsubstituted mercapto group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, alkoxy group, alkoxyalkyl group Carboxyl group, alkoxycarbonyl group, sulfo group and the like. The alkyl group here is the same as the alkyl group of the alkoxycarbonyl group described above, and the acyl group is the same as described above, and the aryl group is aryl. (Aryl) group includes an aromatic ring to water listed in the above-mentioned cyclic hydrocarbon residue. Group excluding the atom. The aryl group may further have a substituent, and examples of the substituent include the same substituents that the above-described cyclic hydrocarbon residue may have. Examples of the halogen atom include atoms such as chlorine, bromine and iodine. Examples of phosphoric acid ester groups include phosphoric acid (C1-C4) alkyl ester groups. Examples of the substituted or unsubstituted mercapto group include a mercapto group and an alkyl mercapto group. Examples of the substituted or unsubstituted amino group include an amino group, a mono- or dialkylamino group, a mono- or diaromatic amino group, and the like, such as a mono- or dimethylamino group, a mono- or diethylamino group, a mono- or dipropylamino group, a mono- or diphenylamino group Groups and mono- or dibenzylamino groups and the like. Examples of the substituted or unsubstituted amide group include an amide group, an alkylamide group, and an aromatic amide group. Examples of the alkoxy group include C1-C10 alkoxy groups. Examples of the alkoxyalkyl group include (C1-C10) alkoxy (C1-C4) alkyl groups. Examples of the alkoxycarbonyl group include C1-C10 alkoxycarbonyl groups. Acidic groups such as carboxyl group, sulfo group and phosphoric acid group are metal salts such as lithium, sodium, potassium, magnesium and calcium, and quaternary ammonium salts such as tetramethylammonium, tetrabutylammonium, pyridinium and imidazolium. The salt may be formed.

The heterocyclic residue represented by A ₁ and A ₂ in Formula (2) means a group obtained by removing one hydrogen atom from a heterocyclic compound, and examples of the heterocyclic compound include a pyridine ring and a pyrazine ring. , Pyrimidine ring, pyrazole ring, pyrazolidine ring, thiazolidine ring, oxazolidine ring, pyran ring, chromene ring, pyrrole ring, benzimidazole ring, imidazoline ring, imidazolidine ring, imidazole ring, pyrazole ring, triazole ring, triazine ring, diazole ring , Morpholine ring, indoline ring, thiophene ring, bithiophene ring, terthiophene ring, furan ring, oxazole ring, thiazine ring, thiazole ring, indole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, indolenine Ring, benzoindolenin ring, Rajin ring, a quinoline ring, a quinazoline ring, a carbazole ring, and the like may be respectively increased ring or hydrogenation. The heterocyclic residue may have a substituent, and examples of the substituent include the same substituents that the above-described cyclic hydrocarbon residue may have.
Preferred examples of the heterocyclic residue represented by A ₁ and A ₂ include a pyridine ring, a pyrazine ring, a piperidine ring, a morpholine ring, an indoline ring, a thiophene ring, a furan ring, an oxazole ring, a thiazole ring, an indole ring, and a benzothiazole. And a group obtained by removing one hydrogen atom from a heterocyclic compound such as a ring, a benzoxazole ring, a pyrazine ring, and a quinoline ring.

The amino group represented by A ₁ and A ₂ in Formula (2) may have a substituent. Examples of the amino group having a substituent include a mono- or dialkylamino group, a mono- or diaromatic amino group, and a monoalkyl monoaromatic amino group. The alkyl group possessed by the alkylamino group includes the alkoxycarbonyl group described above. The same thing as the alkyl group which this has, and the same thing as the above-mentioned cyclic hydrocarbon residue are mentioned as an aromatic which an aromatic amino group has. Specific examples of the amino group having a substituent include a mono- or dimethylamino group, a mono- or diethylamino group, a mono- or dipropylamino group, a mono- or diphenylamino group, and a mono- or dibenzylamino group.
Examples of the alkyl group represented by A ₁ and A ₂ in Formula (2) include the same alkyl groups as the above-described alkoxycarbonyl group, and the alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include an aryl group, a halogen atom, and an alkoxy group. Examples of these aryl groups and halogen atoms are the same as those described above, and examples of the alkyl group that the alkoxy group has are the same as the alkyl groups that the alkoxycarbonyl group has.

A ₁ and A ₂ may be combined to form a ring.
N in Formula (2) represents an integer of 1 to 6, and when n is 2 or more and there are a plurality of A ₁ and A ₂ , any two of them may combine to form a ring. Good. When it forms a ring, but any of A ₁ and the one of A ₂ is not limited particularly either binding, usually adjacent A ₁ and A ₂ or two adjacent of A ₁ between or two adjacent A ₂ A ring is formed with each other. The ring may have a substituent. Examples of the substituent in the case of having a substituent include the same substituents that the above-described cyclic hydrocarbon residue may have. Examples of the ring formed by combining any _two of A ₁ and A ₂ or a plurality of A ₁ and a plurality of A ₂ include an unsaturated hydrocarbon ring or a heterocyclic ring. Examples of unsaturated hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, pyrene, indene, azulene, fluorene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene, and cyclopentadiene. As the heterocyclic ring, pyridine ring, pyrazine ring, indoline ring, thiophene ring, furan ring, pyran ring, oxazole ring, thiazole ring, indole ring, benzothiazole ring, benzoxazole ring, pyrazine ring, quinoline ring, carbazole ring, A benzopyran ring etc. are mentioned. Of these, preferred examples include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a pyran ring. In addition, when A ₁ or A ₂ has a carbonyl group or a thionyl group, a cyclic ketone or a cyclic thioketone may be formed.

Preferable examples of A ₁ and A ₂ include independently a carboxyl group, cyano group, alkoxycarbonyl group, acyl group, hydroxyl group, hydrogen atom, halogen atom, and alkyl group. More preferably, a carboxyl group, a cyano group, a hydrogen atom, a halogen atom, and an alkyl group are mentioned. Of the halogen atoms, a chlorine atom, a bromine atom, and an iodine atom are preferable. Further, Equation (2) A ₁ that bind to the same carbon atom to the carboxyl group are specified in the _(specified has been closest A ₁ to the carboxyl _groups) is particularly preferably a carboxyl group or a cyano group.

  X represents an aromatic hydrocarbon residue, a heterocyclic residue or an amino group. An aromatic hydrocarbon residue means a group obtained by removing one hydrogen atom from an aromatic hydrocarbon, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, indene ring, azulene ring, fluorene ring, etc. A group obtained by removing one hydrogen atom from an aromatic hydrocarbon can be mentioned, and is usually an aromatic hydrocarbon residue having a C6-C16 aromatic ring (such as an aromatic ring and a condensed ring containing an aromatic ring). Any of these may have a substituent.

Examples of the heterocyclic residue represented by X in Formula (2) include a group in which one hydrogen atom has been removed from a heterocyclic compound. Examples of the heterocyclic compound include pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, pyrazolidine ring, thiazolidine ring, oxazolidine ring, pyran ring, chromene ring, pyrrole ring, benzimidazole ring, imidazoline ring, imidazolidine ring, Imidazole ring, pyrazole ring, triazole ring, triazine ring, diazole ring, morpholine ring, indoline ring, thiophene ring, bithiophene ring, terthiophene ring, furan ring, oxazole ring, thiazine ring, thiazole ring, indole ring, benzothiazole ring, A naphthothiazole ring, a benzoxazole ring, a naphthoxazole ring, an indolenine ring, a benzoindolenin ring, a pyrazine ring, a quinoline ring, a quinazoline ring, a carbazole ring, and the like, each of which may be increased or hydrogenated, It may have a substituent. Further, when X is a heterocyclic residue, the heterocyclic ring may be quaternized and may have a counter ion. The counter ion is not particularly limited and may be a general anion. Specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hydroxide ion, methyl sulfate ion, toluenesulfonate anion, tetrafluoroborate anion, hexafluorophosphonate anion. , Thiocyanate anion, tetracyanoborate anion, dicyanoimide anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, N-trifluoromethanesulfonyl-N-pentafluoroethanesulfonyl ) Anion anion, bromide ion, iodide ion, perchlorate ion, tetrafluoroborate anion, hexafluorophosphonate anion, Ene sulfonate anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl) imide anion is preferable. Moreover, you may neutralize by acidic groups, such as a carboxyl group in the molecule | numerator or between molecule | numerators instead of a counter ion.
The amino group represented by X in Formula (2) may have a substituent. Specific examples of the amino group which may have a substituent include an amino group, a diphenylamino group, a monophenylamino group, a dialkylamino group, a monoalkylamino group, an alkylphenylamino group, an alkoxyamino group, an acylamino group ( Examples thereof include a benzoylamino group and an acetylamino group. Examples of the alkyl group, alkoxy group, acyl group and the like of these amino groups are the same as those described above.

X may combine with A ₁ or A ₂ to form a ring, and the formed ring may have a substituent. Examples of the ring formed by combining X with A ₁ or A ₂ include, for example, a benzene ring, naphthalene ring, indene ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, thiophene ring, indolenine ring, and benzoindolenine. Ring, pyrazole ring, pyrazolidine ring, thiazole ring, thiazolidine ring, benzothiazole ring, oxazole ring, oxazolidine ring, benzoxazole ring, pyran ring, chromene ring, pyrrole ring, imidazole ring, benzimidazole ring, imidazoline ring, imidazolidine ring , An indole ring, a furan ring, a carbazole ring, a pyran ring, a benzopyran ring, a phthalocyanine ring, a porphyrin ring, a ferrocene, and the like, each of which may be hydrogenated.

Substituent in the case where the aromatic hydrocarbon residue or heterocyclic residue in X has a substituent, and substitution in the case of having a substituent on the ring formed from the above two of X, A ₁ or A ₂ the group, the same as the substituents on the mentioned in the paragraph of the previous a ₁ or a ₂ cyclic hydrocarbons, and carbonyl groups, and the like thiocarbonyl group. In addition, when X, A ₁ or A ₂ forming the ring has a carbonyl group or a thiocarbonyl group, the ring formed from two of X, A ₁ and A ₂ is substituted with O =, S It may be a ring substituted with =, ie, a cyclic ketone or a cyclic thioketone. Preferred as a substituent on the above aromatic hydrocarbon residue or heterocyclic residue in X, and a substituent on the ring formed from two of X, A ₁ and A ₂ are the substituents An amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an acetyl group which may have a substituent, a hydroxyl group, a halogen, Atom, O =, S =. More preferably, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, O = and S = may be mentioned. Here, examples of the amino group which may have a substituent include a mono- or dialkyl-substituted amino group, a monoalkylmonoaryl-substituted amino group, a diaryl-substituted amino group, a mono- or dialkylene-substituted amino group, and a dialkyl A substituted amino group and a diaryl-substituted amino group are preferred. Examples of the alkyl group which may have a substituent include an aryl-substituted alkyl group, a halogen atom-substituted alkyl group, and an alkoxy-substituted alkyl group. Examples of the alkoxy group which may have a substituent include an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, and an aryl-substituted alkoxy group.

  Particularly preferred examples of X include ethenyl group derivatives having a triphenylamine derivative at the terminal, butadienyl group derivatives, hexatrienyl group derivatives, thiophenyl group derivatives, bithiophenyl group derivatives, terthiophenyl group derivatives, and the like. Any of these derivatives may have a substituent, and the substituent is the same as the substituent when the aromatic hydrocarbon residue or heterocyclic residue in X has a substituent. Is mentioned.

  The dye represented by the formula (2) can take structural isomers such as a cis isomer and a trans isomer, but is not particularly limited, and any of them can be used favorably as a photosensitizing dye.

  Preferable specific examples of such a sensitizing dye include, for example, International Patent Publication WO2002 / 011213, Japanese Patent Application Laid-Open No. 2003-171146, Japanese Patent Application Laid-Open No. 2003-282165, International Patent Application Publication No. WO2004 / 082061, and Japanese Patent Application Laid-Open No. 2004/082061. Examples thereof include dyes described in Japanese Patent Application Laid-Open No. 2006-134649, Japanese Patent Application Laid-Open No. 2006-079898, International Publication No. WO2007 / 100033, Japanese Patent Application Laid-Open No. 2007-149570, and the like.

The dye-sensitized solar cell of the present invention has a second conductive support having a counter electrode.
The second conductive support includes platinum that acts as a counter electrode on the surface of the same conductive support as that used for the first conductive support and catalytically acts on the reduction reaction of the redox electrolyte as a counter electrode. Carbon, rhodium, ruthenium, or the like, or those obtained by applying and firing fine particles of the above-mentioned catalytic atoms or conductive fine particle precursors are used.

  The dye-sensitized solar cell of the present invention has an electrolytic solution containing iodine, iodine ions, and a compound represented by the following formula (1) as a charge transfer layer.

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently have an aliphatic hydrocarbon residue having 10 or less carbon atoms and a substituent which may have a substituent. An aromatic hydrocarbon residue that may be substituted, a heterocyclic residue that may have a substituent, an oxygen atom that may have a covalent bond with another atom, a nitrogen atom that may have a covalent bond with another atom, A sulfur atom, a halogen atom or a hydrogen atom which may have a covalent bond with another atom is represented. In addition, any two members selected from R ₁ , R ₂ , R ₃ and R ₄ may be bonded to form a ring.

The aliphatic hydrocarbon residue having 1 to 10 carbon atoms represented by R _{1 to} R ₄ means a residue obtained by removing one hydrogen atom from an aliphatic hydrocarbon having 1 to 10 carbon atoms. It may be branched or cyclic, and may be any of saturated aliphatic hydrocarbon and unsaturated aliphatic hydrocarbon. The aliphatic hydrocarbon residue having 1 to 10 carbon atoms is, for example, a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, A substituent selected from the group consisting of a group, an isocyano group, a nitro group, a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group. The substitution position and the number of substitutions of the substituent are not particularly limited, and may have a plurality of the same substituents or a plurality of different substituents.

The aromatic hydrocarbon residue represented by R _{1 to} R ₄ means a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon. Examples of the aromatic hydrocarbon include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, an indene ring, an azulene ring, and a fluorene ring, which may each be increased in number. The aromatic hydrocarbon residue may be, for example, a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group The group may have a substituent selected from the group consisting of a group, a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group. The substitution position and the number of substitutions of the substituent are not particularly limited, and may have a plurality of the same substituents or a plurality of different substituents.

The heterocyclic residue represented by R _{1 to} R ₄ means a residue obtained by removing one hydrogen atom from a heterocyclic compound. Examples of the heterocyclic compound include pyrrolidine ring, oxolane ring, thiolane ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, oxane ring, thiane ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiozole. Ring, imidazoline ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, pteridine ring, chromene ring, isochromene ring, acridine A ring, a xanthene ring, a carbazole ring, and the like, and each may be a ring-increased or hydrogenated ring. The heterocyclic residue includes, for example, a halogen atom, an alkoxy group, an ester group, an acyl group, an amino group, an amide group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cyano group, an isocyano group, a nitro group, It may have a substituent selected from the group consisting of a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group. The substitution position and the number of substitutions of the substituent are not particularly limited, and may have a plurality of the same substituents or a plurality of different substituents.

The oxygen atom which may have a covalent bond with other atoms represented by R _{1 to} R ₄ is a free covalent bond with an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue, a hydrogen atom, etc. The oxygen atom which may have is represented.
The nitrogen atom which may have a covalent bond with other atoms represented by R _{1 to} R ₄ is a free covalent bond with an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue and a hydrogen atom. The nitrogen atom which may have is represented.
The sulfur atom that may have a covalent bond with other atoms represented by R _{1 to} R ₄ is a free covalent bond with an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue, a hydrogen atom, or the like. The sulfur atom which may have is represented.
These aliphatic hydrocarbon residue, aromatic hydrocarbon residue and heterocyclic residue are the term of the aliphatic hydrocarbon residue, aromatic hydrocarbon residue and heterocyclic residue represented by R _{1 to} R _4. The same substituents as mentioned can be mentioned.

Further, any two selected from R _{1 to} R ₄ may be bonded to form a ring. The ring that may be formed may be either a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and the ring that may be formed may have any number of substituents at any position.
Examples of the ring that may be formed by R ₂ and R ₃ include, for example, a cyclohexane ring, a cyclopentane ring, a cyclohexene ring, a cyclopentene ring, a cyclohexadiene ring, a cyclopentadiene ring, a lactone ring, a lactam ring, a cyclic ketone, Examples include pyrrolidine ring, piperidine ring, oxolane ring, tetrahydropyran ring, thiolane ring, pentamethylene sulfide ring, morpholine ring, thiomorpholine ring, etc. Good. Examples of the substituent that may have include, for example, a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, Examples thereof include a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group.

Examples of the ring that may be formed by R ₁ and R ₄ include, for example, a cyclic diketone, an oxolactone ring, an oxolactam ring, a dioxopyrrolidine ring, a dioxopiperidine ring, a tetrahydrofurazinone ring, a tetrahydropyrazinone ring, Examples thereof include a dioxothiolane ring and a dioxothian ring, each of which may have a substituent and each may be increased. Examples of the substituent that may have include, for example, a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, Examples thereof include a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group.
Examples of the ring that may be formed by R ₁ (or R ₄ ) and R ₂ (or R ₃ ) include, for example, lactone ring, lactam ring, cyclic ketone, pyrrolidinone ring, piperidinone ring, tetrahydrofuranone ring, tetrahydro Examples include a pyranone ring, an oxothiolane ring, and an oxothian ring, each of which may have a substituent and each may be increased. Examples of the substituent that may have include, for example, a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, Examples thereof include a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group.

Among these, R _{1 to} R ₄ may have a substituent, an aliphatic hydrocarbon having 1 to 10 carbon atoms, an aromatic hydrocarbon residue that may have a substituent, and a common atom. An oxygen atom that may have a bond, a nitrogen atom or a hydrogen atom that may have a covalent bond with another atom, or a saturated hydrocarbon ring or an unsaturated hydrocarbon ring formed by R ₁ and R ₄ It is preferable.
Furthermore, R ₁ and R ₄ are both an aliphatic hydrocarbon having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon residue which may have a substituent. β-diketone, _one of R _{1 and} R ₄ is an oxygen atom that may have a covalent bond with another atom, and the other is an aliphatic hydrocarbon having 1 to 10 carbon atoms that may both have a substituent Or a β-ketoester which is any of aromatic hydrocarbon residues which may have a substituent, and any one of R _{1 and} R ₄ is a nitrogen atom which may have a covalent bond with another atom, Either one of the aliphatic hydrocarbons having 1 to 10 carbon atoms which may have a substituent on the other side, or β ketoamide which is either an aromatic hydrocarbon residue which may have a substituent More preferably. These β-diketone, β-ketoester, and β-ketoamide are organic compounds in which two keto functional groups (carbonyl groups) are bonded to each other with one carbon separated in one molecule.

Preferable specific examples of R _{1 to} R ₄ include compounds represented by the following formulas (1000) to (1128).

  In the dye-sensitized solar cell of the present invention, the compound represented by the formula (1) may be used alone, or two or more kinds may be used in combination. These may be commercially available products or may be synthesized independently, but those having high purity are more preferable, and compounds having high solubility in an electrolyte solution solvent are more preferable. The concentration of these compounds in the electrolytic solution is usually 0.01M to 5M, preferably 0.02 to 3M, more preferably 0.03 to 2M, and particularly preferably 0.05 to 1.

  The electrolyte solution included in the dye-sensitized solar cell of the present invention contains a compound having iodine ions as counter ions. The compound having iodine ions as a counter ion is not particularly limited as long as it is a compound that can provide iodine ions in the electrolytic solution, but it is preferable that the degree of dissociation of iodine ions is high. Preferred examples include metal halide salts such as lithium iodide, sodium iodide, potassium iodide and cesium iodide; or ammonium iodide such as tetrapropylammonium iodide and tetrabutylammonium iodide, imidazolium iodide, 1,3-dimethylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1-methyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, 1-hexyl- 3-methylimidazolium iodide, 1,2-dimethyl-3-propylimidazolium iodide, 1,2-dimethyl-3-butylimidazolium iodide, 1,2-dimethyl-3-hexylimidazolium iodide, etc. The imidazolium Yoda N, N-dimethylpyrrolidinium iodide, N-methyl-N-propylpyrrolidinium iodide, pyrrolidinium iodide such as N, N-dibutylpyrrolidinium iodide, N-methylpyridinium iodide N-propylpyridinium iodide, pyridinium iodide such as N-butylpyridinium iodide, pyrrolium iodide such as 1-ethyl-1-methylpyrrolium iodide, 1-propyl-2-methylpyrazolium iodide And pyrazolium iodide such as tetrabutylphosphonium iodide, and the like. Among these compounds having iodine ions as counter ions, lithium iodide, sodium iodide, potassium iodide, trimethylammonium iodide, tetrabutylammonium iodide, 1,3-dimethylimidazolium iodide, 1-ethyl-3 -Methylimidazolium iodide, 1-methyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, 1,2-dimethyl-3-propylimidazolium iodide and the like are more preferable. A compound having iodine ion as a counter ion may be used alone or in combination of two or more in the electrolyte solution of the dye-sensitized solar cell of the present invention.

The concentration of iodine in the electrolyte solution contained in the electrolyte solution of the dye-sensitized solar cell of the present invention is usually 0.01M to 10M, preferably 0.02 to 5M, more preferably 0.03 to 3M, particularly. Preferably it is 0.05-2M.
Moreover, the density | concentration in the electrolyte solution of the compound which makes iodine ion a counter ion contained in the electrolyte solution which the dye-sensitized solar cell of this invention has is 0.01M-20M normally, Preferably it is 0.02-15M, Furthermore, Preferably it is 0.03-10M, Most preferably, it is 0.05-5M.

  As the solvent of the electrolyte solution of the dye-sensitized solar cell of the present invention, an electrochemically inert solvent is preferably used, and an organic solvent, an ionic liquid, or a mixed solution of an organic solvent and an ionic liquid is generally used. Is. Organic solvents that can be used in combination include acetonitrile, butyronitrile, valeronitrile, hexanenitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol dimethyl ether, and triethylene. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2-dimethoxyethane, γ-butyrolactone, diethyl ether, diethyl carbonate, dimethyl carbonate, dimethylformamide, dimethyl sulfoxide, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3 -Methyl-oxazolidin-2-one, Preferred examples include holane, tetrahydrofuran, sulfolane, methyl isopropyl sulfone and the like. Among these, acetonitrile, valeronitrile, hexane nitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, diethylene glycol dimethyl ether, triethylene Glycol dimethyl ether, 1,2-dimethoxyethane, γ-butyrolactone, sulfolane, methyl isopropyl sulfone and the like are more preferable, acetonitrile, valeronitrile, hexanenitrile, 3-methoxypropionitrile, methoxyacetonitrile, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, 1,2-dimethoxyethane, sulfolane, methyl Isopropyl sulfone is particularly preferred. In addition, the ionic liquid that can be used in combination is preferably a compound that is liquid at room temperature, such as an imidazole cation, a pyrrolidinium cation, a pyridinium cation, a pyrrolium cation, a pyrazolium cation, or a phosphonium cation, and a fluoride. Ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hydroxide ion, methyl sulfate ion, toluenesulfonate anion, tetrafluoroborate anion, tetracyanoborate anion, hexafluorophosphonate anion, tetra Cyanoborate anion, dicyanoimide anion, trifluoromethanesulfonate anion, bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, N- Compounds that combine trifluoromethane sulfonyl -N- pentafluoroethanesulfonyl) imide anion of the anion are preferred. These solvents may be used alone or in combination of two or more. When two or more types are used in combination, the ratio can be arbitrarily selected.

The electrolyte solution of the dye-sensitized solar cell of the present invention may further contain a sulfur-containing compound. Further, among the sulfur-containing compounds, it is more preferably any one of thiocyanate and a compound having a thioester bond.
Examples of the thiocyanate include lithium thiocyanate (LiSCN), sodium thiocyanate (NaSCN), alkali thiocyanate salt such as potassium thiocyanate (K ₄ SCN); alkaline earth metal thiocinnate salt such as magnesium thiocyanate (Mg (SCN) ₂ ); Thiocyanate salts of onium ions such as phosphonium cations and sulfonium cations; thiocyanates of organic cations such as imidazolium cations, ammonium cations, pyrrolium cations, pyrrolium cations, pyrazolium cations, pyrrolidinium cations, pyridinium cations and guanidinium ions Examples of preferred salts include lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, and guanidinium. More preferred are thiocyanate, 1-ethyl-3-methylimidazolium thiocyanate, 1-methyl-3-butylimidazolium thiocyanate, tetrapropyl thiocyanate, and the like.
Examples of the compound having a thioester bond include S-methyl thioacetate, S-methyl thiopropionate, S-methyl thiobutyrate, S-ethyl thioacetate, S-ethyl thiopropionate, S-ethyl thiobutyrate, and S-thiothioacetate. Chain aliphatic thioester compounds such as propyl, thiopropionic acid S-propyl, thiobutyric acid S-propyl; cyclic aliphatic thioester compounds such as homocysteine thiolactone, cithiolone, thiolactone, thiolactam; thioacetic acid S-phenyl, thioacetic acid S Preferred examples include aromatic thioester compounds such as -furfuryl and thiobenzoic acid S-alkyl; thiocholine derivatives such as acetylthiocholine iodide, butyrylthiocholine iodide, and benzoylthiocholine iodide. Published patent WO2014 / 0842 The compound according to 6 JP etc. are preferably used.
These thiocyanate or compounds having a thioester bond may be used alone or in combination of two or more. Moreover, the addition amount of these compounds is 0.01-10M normally, Preferably it is 0.02-5M, More preferably, it is 0.03-3M, Most preferably, it is 0.05-1.5M.

  Furthermore, the electrolytic solution used in the dye-sensitized solar cell of the present invention may contain a nitrogen-containing compound and other additives as necessary. The additive to be used is not particularly limited, and the amount added may be appropriately selected according to the purpose. However, the effect of improving the transport efficiency of the redox couple in the electrolytic solution, the power from the dye to the oxide semiconductor, and the like. It has the effect of promoting valence injection, the effect of preventing reverse electron transfer from oxide semiconductors, etc., which increases the efficiency of dye-sensitized solar cells, and improves the stability of electrolytes to improve the durability of dye-sensitized solar cells It is preferable to add one that enhances the properties. Moreover, when adding basic compounds, such as a nitrogen-containing compound, it is preferable that it is a compound with low basicity.

  The sealing agent of the dye-sensitized solar cell of the present invention is used for the purpose of laminating the first and second conductive supports and sealing the electrolytic solution used in the charge transfer layer. The sealing agent is not particularly limited as long as it fulfills the above-mentioned purpose, and specifically, an epoxy resin-based sealing agent, an acrylate resin-based sealing agent, a silicone resin-based sealing agent, a polyisobutylene resin-based sealing agent, and an ionomer. Examples thereof include resin-based sealing agents and (modified) olefin resin-based sealing agents. Among these, an epoxy resin sealant having strong adhesive strength and excellent solvent resistance and iodine resistance is preferably used.

  As the epoxy resin-based sealant, any of thermosetting type, ultraviolet curable type and photothermal combination type sealant can be used, but it can be applied to screen printing method and dispensing method. A sealing agent having excellent properties, moisture resistance, solvent resistance, light resistance, gas barrier properties and the like is preferable. The epoxy resin contained in the epoxy resin-based sealing agent is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. For example, a novolac type epoxy resin, a bisphenol type epoxy resin, a biphenyl type epoxy Resin, triphenylmethane type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, diglycidyl etherified product of bifunctional phenol, diglycidyl etherified product of bifunctional alcohol, other glycidyl ether type Examples thereof include an epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, an alicyclic epoxy resin, a halide thereof, a hydrogenated product, and the like. Among them, phenol novolak, cresol novolak, bisphenol A type novolak, trisphenol methane novolak, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, tetrabromobisphenol A, terpene diphenol, 4,4'-biphenol, 2,2 '-Biphenol, 3,3', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and phenol (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) Formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4 , 4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4-bis (chloromethyl) benzene, polycondensates with 1,4-bis (methoxymethyl) benzene and the like, and modified products thereof Preferred are solid or liquid epoxy resins such as glycidyl etherified epoxy resins, glycidyl aminated epoxy resins, glycidyl esterified epoxy resins, and their halides and hydrogenated products, such as phenol novolac and cresol novolac. More preferred are trisphenol methane novolak, bisphenol A type novolak, bisphenol A, bisphenol F, bisphenol S, resorcin, glycidyl etherified epoxy resins of fluorene bisphenol, and their halogenated and hydrogenated epoxy resins. Type epoxy resin, cresol novolac type epoxy resin, trisphenol methane novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcing ricidyl ether, and their halides, hydrogenated products A certain epoxy resin is particularly preferable, and a trisphenol novolac type epoxy resin and a bisphenol A type epoxy resin are most preferable. These may be used alone or in combination of two or more. The epoxy resin as described above is useful for adjusting the viscosity of the sealant, and the sealant using these epoxy resins is used to superimpose the substrates at room temperature when creating the dye-sensitized solar cell of the present invention. And facilitates gap formation.

The composition of the epoxy resin-based sealant is not particularly limited. For example, if it is a thermosetting sealant, it includes an epoxy resin and a thermosetting agent, and the ultraviolet curable sealant includes an epoxy resin and a photopolymerization initiator. As the curable sealant used in combination with photothermal heat, an epoxy resin, a thermosetting agent and a photoreaction initiator are generally used. Any composition may contain further additives. For example, if it is a thermosetting type sealant, other thermosetting resins, reaction accelerators, fillers, coupling agents, solvents, stress relaxation agents, viscosity adjustments. If it is an ultraviolet curable sealant, such as an agent, pigment, leveling agent, antifoaming agent, spacer, etc., other ultraviolet curable resins, photosensitizers, ion catchers, fillers, coupling agents, solvents, stress relaxation If it is a photo-heat combined curable sealant, such as an agent, viscosity modifier, pigment, leveling agent, antifoaming agent, spacer, etc., other thermosetting resins, other ultraviolet curable resins, reaction accelerators, photosensitization An agent, an ion catcher, a filler, a coupling agent, a solvent, a stress relaxation agent, a viscosity modifier, a pigment, a leveling agent, an antifoaming agent, a spacer and the like may be contained as necessary. Among these, a thermosetting epoxy resin-based sealing agent is preferably used, and further includes a thermosetting epoxy resin system containing phenol, polyphenol, bisphenol, novolac, amine, guanamine, imidazole, hydrazide, acid anhydride, and the like as a thermosetting agent. Sealing agents are more preferable, and among them, thermosetting epoxy resin-based sealing agents containing novolak and hydrazide are particularly preferable, and thermosetting epoxy resin-based sealing agents containing phenol novolak, aromatic hydrazide, and aliphatic hydrazide having 6 or more carbon atoms. Is most preferred. These thermosetting agents may be used independently and may use 2 or more types together. The epoxy resin-based sealing agent as described above is excellent in adhesiveness, moisture resistance, solvent resistance, and the like, and can particularly improve the durability of the dye-sensitized solar cell of the present invention.
Specific examples of the epoxy resin-based sealant include Japanese Patent Application Laid-Open No. 2002-368236, International Patent Publication No. 2004/075333, International Patent Publication WO2007 / 046499, International Patent Publication WO2007 / 007671, International Patent Publication WO2011 / 145551, and the like. Can be exemplified. Among these, the sealing agents described in JP-A No. 2002-368236 and International Patent Publication WO 2011/145551 are particularly preferable.

  Next, a general method for producing the dye-sensitized solar cell of the present invention will be described. First, a thin film (semiconductor-containing layer) of oxide semiconductor fine particles is formed on the conductive support described above. A thin film of oxide semiconductor fine particles is a method of forming a thin film of semiconductor fine particles by directly applying oxide semiconductor fine particles onto a conductive support by spray spraying or the like. A method of depositing into a thin film, a slurry containing fine particles obtained by hydrolyzing a semiconductor fine particle slurry or a semiconductor fine particle precursor such as semiconductor alkoxide, and the like. It can be manufactured by a firing method or the like. In view of the performance of the electrode using an oxide semiconductor, a method using a slurry is preferable. In the case of this method, the slurry is obtained by dispersing the oxide semiconductor fine particles, which are secondarily aggregated, in a dispersion medium by an ordinary method so that the average primary particle diameter is 1 to 200 nm.

  The dispersion medium for dispersing the slurry is not particularly limited as long as the semiconductor fine particles can be dispersed. Examples thereof include water, alcohols such as ethanol, ketones such as acetone and acetylacetone, hydrocarbons such as hexane, and the like. You may mix and use. Furthermore, water is preferably used because it suppresses a change in viscosity of the slurry. In addition, a dispersion stabilizer can be used in combination for the purpose of stabilizing the dispersion state of the oxide semiconductor fine particles. Examples of the dispersion stabilizer used include acids such as acetic acid, hydrochloric acid and nitric acid, and organic solvents such as acetylacetone, acrylic acid, polyethylene glycol and polyvinyl alcohol.

  The substrate coated with the slurry may be fired, and the firing temperature is usually 100 ° C. or higher, preferably 200 ° C. or higher, and the upper limit is generally below the melting point (softening point) of the substrate material, usually 900 ° C. or lower, preferably Is 600 ° C. or lower. The firing time is not particularly limited, but is preferably within 4 hours. The thickness of the thin film on the substrate is usually 1 to 200 μm, preferably 1 to 50 μm.

  The thin film of oxide semiconductor fine particles may be subjected to secondary treatment. For example, improving the performance of thin film of semiconductor fine particles by directly immersing the thin film together with the substrate in a solution of the same metal alkoxide, chloride, nitride or sulfide as the semiconductor and drying or refiring. You can also. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin, and alcohol solutions thereof are used. Examples of the chloride include titanium tetrachloride, tin tetrachloride, zinc chloride and the like, and an aqueous solution thereof is used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

Next, the sensitizing dye is adsorbed on the oxide semiconductor thin film. Examples of the method for adsorbing the sensitizing dye include a method in which the conductive support provided with the semiconductor-containing layer is immersed in a solution obtained by dissolving a dye in a solvent or a dispersion obtained by dispersing the dye in a solvent. The concentration of the dye in the solution or dispersion may be determined as appropriate depending on the type and solubility of the dye. The immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time is about 1 to 72 hours. Solvents that can be used to dissolve the sensitizing dye include, for example, methanol, ethanol, acetonitrile, acetone, dimethyl sulfoxide, dimethylformamide, n-propanol, i-propanol, t-butanol, tetrahydrofuran, and the like. May be used alone or in admixture of two or more at any ratio. The concentration of the sensitizing dye in the solution is usually 1 × 10 ^{−6 to} 1M, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ M. Thus, the electroconductive support body which has a semiconductor content layer sensitized with the pigment | dye is obtained by immersing the electroconductive support body in which the semiconductor content layer was provided with the sensitizing dye.

  The ratio of each dye in the case of using a mixture of dyes is not particularly limited, but generally it is preferable to use each dye at least about 10 mol% or more. When the dye is supported on the semiconductor-containing layer using a solution in which two or more kinds of dyes are dissolved or dispersed, the total concentration of the dyes in the solution may be the same as when only one kind is supported. The solvent used may be the same or different.

  When the dye is supported on the semiconductor-containing layer, it is effective to support the dye in the presence of the inclusion compound in order to prevent the association of the dyes. Examples of the clathrate compound used here include steroidal compounds such as cholic acid, crown ether, cyclodextrin, calixarene, polyethylene oxide and the like. Cholic acid is preferably used. Cholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, ursodeoxycholic acid, lithocholic acid and the like are preferably used, and deoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid and lithocholic acid are more preferably used. These inclusion compounds may be added to the dye solution, or the dye may be dissolved or dispersed after the inclusion compound is previously dissolved in a solvent. Two or more of these inclusion compounds can be used in combination, and the ratio thereof can be arbitrarily selected. Further, after the dye is supported, the semiconductor-containing layer may be treated with an amine compound such as 4-t-butylpyridine, pyridine, 4-methylpyridine, or triethylamine, or an acid such as formic acid, acetic acid, or propionic acid. The treatment method includes, for example, a method in which a conductive support provided with a semiconductor-containing layer carrying a sensitizing dye is immersed in an ethanol solution to which an amine compound or an acid is added, or a semiconductor-containing layer carrying a sensitizing dye is provided. For example, a method in which an amine compound or an acid is directly brought into contact with the conductive support, followed by washing and drying with an organic solvent, water, or the like after a certain time is employed.

  Next, a conductive support (first conductive support) having a semiconductor-containing layer sensitized with the dye obtained as described above and a conductive support (second conductive) having a counter electrode. A method of bonding the support) to the support using a sealant will be described. First, a sealant to which a spacer (gap control material) is added is dispenser, screen printing machine, ink jet printing machine, etc. leaving the injection port of the charge transfer layer around the conductive surface of one of the conductive supports. In the case where the sealing agent contains a solvent after being applied in the form of a weir, the solvent is evaporated by heating with, for example, a hot air dryer or the like, and then the conductive surfaces of the first and second conductive supports are The other conductive support is superposed so as to face each other, and the sealing agent is cured by heating and / or ultraviolet irradiation. As the spacer used here, for example, glass fiber, silica beads, polymer beads and the like, and fine particles coated with metal such as gold pearl and silver pearl are used. The diameter varies depending on the purpose, but is usually 1 to 100 μm, preferably 10 to 40 μm. The usage-amount is 0.1-10 mass parts normally with respect to 100 mass parts of sealing agents, Preferably it is 0.5-5 mass parts, More preferably, it is 1-2.5 mass parts. The conditions for heat-curing the sealant are usually 90 to 180 ° C. for 1 to 3 hours. As a heat curing method, a method of sandwiching with a hot press machine having two hot plates, a method of performing in an oven after fixing with a jig, or the like can be adopted. Moreover, what is necessary is just to select the irradiation conditions of the ultraviolet-ray in the case of using a ultraviolet curing type and a photothermal combined curing type sealing agent according to the curing rate of a sealing agent. The gap between the first and second conductive supports is usually 1 to 100 μm, preferably 4 to 50 μm.

  The dye-sensitized solar cell of the present invention can be obtained by injecting the charge transfer layer into the gap between the pair of conductive supports bonded together as described above and then sealing the injection port of the charge transfer layer. Isobutylene resin, epoxy resin, UV curable acrylic resin, etc. can be used as the sealant (sealing agent) for sealing the charge transfer layer injection port, but the effect of preventing the charge transfer layer from leaking from the injection port As long as it has, it can use not only the above-mentioned. As a sealing agent used, a commercial item may be sufficient and UV curable acrylic resin is preferable.

  On the other hand, as another method for producing a dye-sensitized solar cell, as described in International Publication No. WO2007 / 046499, a charge transfer layer injection port is provided at the periphery of the conductive surface of one of the conductive supports. Without providing a sealing agent weir, and then placing a charge transfer layer similar to the above inside the sealing agent weir so that the conductive surfaces of the first and second conductive supports face each other under reduced pressure. A method of obtaining a dye-sensitized solar cell by forming a gap at the same time as mounting and bonding the conductive support, and then curing the sealant can also be employed.

  FIG. 1 is a schematic cross-sectional view of an essential part for explaining the structure of a dye-sensitized solar cell of the present invention, wherein 1 is a first conductive support having conductivity inside, and 2 is a semiconductor sensitized by the dye. The inclusion layers 1 and 2 are collectively referred to as an oxide semiconductor electrode. 3 is a second conductive support having a counter electrode in which platinum or the like is disposed on a conductive surface inside the conductive support, 4 is a charge transfer layer disposed in a gap between the pair of conductive supports, 5 is a sealing agent, and 6 is a glass substrate.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Electrolyte preparation example 1
0.1M iodine, 0.1M lithium iodide (LiI) as iodide and 1.2M 1-methyl-3-propylimidazolium iodide, 0.1M guanidine thiocyanate as thiocyanate compound, formula as additive Each component is dissolved and mixed in 3-methoxypropionitrile so that acetylacetone (1000), which is a compound represented by (1), has a concentration of 0.5 M, and the dye-sensitized solar cell electrolyte 1 ( Table 1 below, used in Example 1).

Electrolyte preparation examples 2-6
Except that the additives were changed to the respective compounds shown in Table 1, according to Electrolytic Solution Preparation Example 1, electrolytes 2 to 6 for dye-sensitized solar cells (used in Table 1, Example 2 to Comparative Example 3 below) ) Respectively.

Electrolyte preparation example 7
Except that the compound represented by the formula (1) was not used as an additive, an electrolytic solution 7 for dye-sensitized solar cell (used in Table 1 and Comparative Example 4 below) was obtained according to Electrolytic Solution Preparation Example 1. It was.

Electrolyte preparation example 8
0.1M iodine, 0.05M lithium iodide (LiI) as iodide and 1.2M 1-methyl-3-propylimidazolium iodide, and 0.1% butyrylthiocholine iodide as a compound having a thioester bond. 05M, 1,3-cyclohexanedione (1089) which is a compound represented by the formula (1) as an additive was dissolved and mixed in 3-methoxypropionitrile so that the concentration became 0.5M. Thus, an electrolyte solution 8 for dye-sensitized solar cells (used in Table 1 and Example 4 below) was obtained.

Electrolyte preparation example 9
Except that the compound represented by the formula (1) was not used as an additive, an electrolytic solution 9 for dye-sensitized solar cell (used in Table 1 and Comparative Example 5 below) was obtained according to Electrolytic Solution Preparation Example 8. It was.

Electrolyte preparation example 10
Each component is dissolved and mixed in 3-methoxypropionitrile so that the concentration of iodine is 0.1M, pyridine is 2.6M, and acetylacetone is 0.3M. 1, used in Comparative Example 6) (PyI ₂ AcacE electrolytic solution described in Non-Patent Document 3).

Example 1
On a conductive surface of an FTO conductive glass support, which is a conductive support, TiO ₂ fine particles (average particle size 20 nm) made into a paste with terpineol were applied with a screen printer and baked at 450 ° C. for 30 minutes. Then, a conductive support having a semiconductor-containing layer (film thickness: 10 μm, minor axis width: 5 mm, major axis width: 4 cm) was prepared. The conductive support provided with the obtained semiconductor-containing layer was treated with 1.6 × 10 ⁻⁴ M of a dye represented by the following formula (3) described in Example 6 of International Publication No. WO2007 / 100033. An oxide semiconductor electrode was prepared by immersing in a dye solution obtained by dissolving in acetone so as to have a concentration of 24 hours at room temperature. Next, Pt was vapor-deposited on the conductive surface of another FTO conductive glass support to produce a counter electrode. Sealing agent obtained by adding 2.5% by mass of gold pearl (pearl diameter 20 μm) as a spacer to the epoxy-based sealing agent described in Sealing Agent Preparation Example 3 of International Patent Publication WO2011 / 14551 at the peripheral edge of the obtained counter electrode Was applied using a screen printer so as to leave the injection port of the charge transfer layer, and then the solvent was removed by heating at 90 ° C. for 18 minutes with a hot air dryer. Thereafter, the above oxide semiconductor electrode was overlaid on the sealant so that the conductive surface of the counter electrode and the semiconductor-containing layer face each other, and was heated at 150 ° C. at a pressure of 2.5 kg / cm ² using a hot press. Was cured for 60 minutes to obtain a cell in which both conductive supports were bonded together. The electrolyte solution 1 obtained in the electrolyte preparation example was filled into the cell from the injection port of the obtained cell, and then the injection port was sealed with a UV curable acrylic resin to thereby provide the dye-sensitized solar cell of the present invention. (Battery 1) was obtained.

Examples 2 and 3
A dye-sensitized solar cell (batteries 2 and 3) of the present invention was obtained in the same manner as in Example 1 except that the electrolytic solution 1 was changed to the electrolytic solutions 2 and 3 obtained in the electrolytic solution preparation example.

Comparative Examples 1-4
Dye-sensitized solar cells for comparison (batteries 4 to 7) were obtained in the same manner as in Example 1 except that the electrolytic solution 1 was changed to the electrolytic solutions 4 to 7 obtained in the electrolytic solution preparation example.

Evaluation test (output measurement of dye-sensitized solar cell)
The batteries 1 to 3 obtained in Examples 1 to 3 and the batteries 1 to 4 obtained in Comparative Examples 1 to 4 were measured for photoelectric conversion ability. 1 kW xenon lamp (manufactured by WACOM) is used as the light source, it is set to 100 mW / cm ² through the AM1.5 filter, and is calculated from the short circuit current density calculated from the short circuit current, effective area, open circuit voltage, short circuit current, and form factor. The photoelectric conversion efficiency was measured using a solar simulator (WXS-155S-10, manufactured by WACOM). The results are shown in Table 2.

In the output measurement of the dye-sensitized solar cell, the batteries 1, 2 and β of the present invention containing acetylacetone or 1,3-cyclohexanedione as β-diketone as additives in addition to iodine, iodide and thiocyanate compound in the electrolyte. All the batteries 3 of the present invention containing methyl acetoacetate, which is a ketoester, have high short-circuit current density and good photoelectric conversion efficiency. On the other hand, comparative batteries 4 and 5 containing simple ketones such as acetone and cyclohexanone as additives in the electrolytic solution, and comparative battery 6 containing simple esters such as ethyl acetate, and a comparative battery containing no additives. All of the batteries 7 had a low short-circuit current density, and the photoelectric conversion efficiency was inferior to that of the battery of the present invention.
Furthermore, the battery 8 (Example 4) of the present invention containing a compound having iodine, iodide, and a thioester bond in the electrolytic solution and containing 1,3-cyclohexanedione as an additive is also included for comparison. The short circuit current density was higher than that of the battery 9 (Comparative Example 5), and the photoelectric conversion efficiency was also good.
In addition, the battery 10 (Comparative Example 6) using the electrolytic solution containing iodine, pyridine, and β-diketone acetylacetone described in Non-Patent Document 3 has a low short-circuit current density and a low photoelectric conversion efficiency. The result was different from that of the sensitized solar cell.
From the above results, it is clear that the dye-sensitized solar cell of the present invention using the electrolytic solution containing the compound represented by the formula (1) has excellent short-circuit current density and photoelectric conversion efficiency. .

  The dye-sensitized solar of the present invention, wherein the dye is a non-metal complex organic dye and the charge transfer layer is an electrolytic solution containing a compound containing iodine, iodine ion and a compound represented by formula (1) The battery has a high short-circuit current density and excellent photoelectric conversion efficiency. For this reason, it is possible to provide a battery having excellent photoelectric conversion efficiency, which is a dye-sensitized solar cell using a non-metal complex dye having few resource restrictions and a wide range of molecular design.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Semiconductor containing layer sensitized with pigment | dye 3 Counter electrode 4 Charge transfer layer 5 Sealing agent 6 Glass substrate

Claims (10)

A first conductive support having a semiconductor-containing layer sensitized by a dye, and a second conductive support having a counter electrode provided at a position where the semiconductor-containing layer and the counter electrode face each other at a predetermined interval A charge transfer layer sandwiched in the gap between the first and second conductive supports, and a sealant provided on the periphery of the first and second conductive supports to seal the charge transfer layer A dye-sensitized solar cell comprising: a dye-sensitized solar cell, wherein the dye is a non-metallic complex organic dye, and the charge transfer layer further contains iodine, iodine ions, and a compound represented by the following formula (1): Sensitive solar cell.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group or aryl group , A cyano group, an isocyano group, a nitro group, a nitroso group, a hydroxyl group, a phosphate ester group, a sulfinyl group, and a sulfonyl group, which may have one or more substituents selected from the group consisting of 1 to 10 carbon atoms Aliphatic hydrocarbon residue, halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, nitroso group, hydroxyl It may have one or more substituents selected from the group consisting of a group, a phosphate ester group, a sulfinyl group and a sulfonyl group. Aromatic hydrocarbon residue, halogen atom, alkoxy group, ester group, acyl group, amino group, amide group, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, isocyano group, nitro group, nitroso group, hydroxyl A heterocyclic residue which may have one or more substituents selected from the group consisting of a group, a phosphate ester group, a sulfinyl group and a sulfonyl group, the aliphatic hydrocarbon residue, the aromatic hydrocarbon residue, An oxygen atom which may have a covalent bond with one or more substituents selected from the group consisting of a heterocyclic residue and a hydrogen atom, the aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue And a nitrogen atom which may have a covalent bond with one or more substituents selected from the group consisting of hydrogen atoms, the aliphatic hydrocarbon residues, aromatic hydrocarbon residues, heterocyclic residues and water One or more substituents covalently bonded may have a sulfur atom selected from the group consisting of atoms, a halogen atom or a hydrogen atom. In addition, selected from R _{1, R 2,} R ₃ and R ₄ Any two of them may combine to form a ring.) The dye-sensitized solar cell according to claim 1, wherein the compound represented by formula (1) is one or more selected from the group consisting of β diketone, β keto ester, and β ketoamide. The dye-sensitized solar cell according to claim 1 or 2, wherein the content of the compound represented by the formula (1) in the charge transfer layer is 0.01 to 5M. The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the sulfur-containing compound is contained in the charge transfer layer. The dye-sensitized solar cell according to claim 4, wherein the sulfur-containing compound contained in the charge transfer layer is either a thiocyanate or a compound having a thioester bond. The dye-sensitized solar cell according to any one of claims 1 to 5, wherein the sealant is an epoxy resin sealant. The dye-sensitized solar cell according to any one of claims 1 to 6, wherein the semiconductor of the semiconductor-containing layer is particulate titanium oxide or particulate composite titanium oxide. Non-metallic complex organic dye is represented by the following formula (2)

(In the formula, A ₁ and A ₂ are each independently a carboxyl group, a cyano group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyclic hydrocarbon residue, a heterocyclic residue, an amino group, a hydroxyl group, a hydrogen atom, Represents a halogen atom or an alkyl group, X represents an aromatic hydrocarbon residue, a heterocyclic residue, or an amino group, n represents an integer of 1 to 6. n is 2 or more, and A1 and A2 are plural. When present, each A ₁ and each A ₂ each independently represents the same or different group, and when a plurality of A ₁ or A ₁ are present, each A ₁ , A ₂ Or when _two or more A ₂ are present, _two of each A ₂ and X may combine to form a ring.)
The dye-sensitized solar cell according to claim 1, having a structure represented by: The dye-sensitized solar cell according to claim 8, wherein A ₁ in Formula (2) is a cyano group or a carboxyl group.   The dye-sensitized solar cell according to claim 8 or 9, wherein X in the formula (2) is a (poly) ethenyl group or a (poly) thiophenyl group having a triphenylamine derivative.

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