JP2007265776A - Flexible dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high performance flexible dye-sensitized solar cell. <P>SOLUTION: The flexible dye-sensitized solar cell comprises at least a semiconductor layer modified with a sensitizer installed on a metal foil; an electrolyte layer containing at least a substance showing reversible electrochemical oxidation reduction characteristics; and a counter electrode in which a bus bar comprising a mixture containing at least a substance having a catalytic action to the substance showing the reversible electrochemical oxidation reduction characteristics and metal particles is fixed to a transparent substrate by a screen printing method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flexible dye-sensitized solar cell having a novel configuration.

Since the dye-sensitized solar cell has been proposed by Gretzel et al. (See, for example, Non-Patent Document 1 and Patent Documents 1 and 2), it can be manufactured with an inexpensive material and a simple process. The practical use is expected as a cost solar cell.
On the other hand, in order to diversify the usage forms of solar cells, development of film-like flexible solar cells has been actively conducted. However, in a general dye-sensitized solar cell, when forming a semiconductor layer made of titanium oxide nanoparticles on a transparent conductive substrate, in order to improve necking between the nanoparticles, the temperature is about 400 to 600 ° C. Because it is fired at a high temperature, it has been virtually impossible to produce a flexible solar cell using a film-like substrate such as plastic. Thus, many attempts have been made to fabricate a semiconductor layer at a low temperature at which a plastic substrate can be used (for example, see Non-Patent Documents 2 and 3), but the performance is low compared to conventional high-temperature firing types. There was a problem.

In order to solve the problem, as shown in Patent Document 3, a semiconductor layer is formed on a metal foil, a film-like plastic electrode is used as a counter electrode, and light is irradiated from the counter electrode side. Attempts have been made to produce dye-sensitized solar cells. However, this configuration has a problem that the amount of light incident on the semiconductor layer is reduced by the catalyst layer provided on the counter electrode, and the efficiency is lowered.
Moreover, when enlarging an element, in order to make the electrical resistance of a transparent electrode small, measures, such as providing a metal bus bar on a transparent electrode, are made | formed (for example, refer patent documents 4-7). If this is applied to the counter-illumination type element, there is a problem that the amount of light incident on the semiconductor layer is further reduced, leading to a reduction in efficiency.

U.S. Pat. No. 4,190,950 WO94 / 04497 pamphlet JP-A-11-288745 JP 2003-203681 A JP 2003-203682 A JP 2003-203683 A JP 2004-164970 A “Nature” (UK), 1991, Vol. 353, p. 737-740 “Journal of Photochemistry and Photobiology A: Chemistry” (Netherlands), 2001, vol. 145, p. 107 “Chemistry Letters”, 2002, p. 1250

  The present invention has been made in view of such a situation, and an object thereof is to provide a high-performance flexible dye-sensitized solar cell.

As a result of intensive studies on the above problems, the present inventors have completed the present invention.
That is, the present invention provides a semiconductor layer modified with a sensitizer provided on a metal foil, an electrolyte layer containing a substance exhibiting at least reversible electrochemical redox characteristics, and the reversible electrochemical redox A flexible dye-sensitized type comprising at least a counter electrode in which a bus bar made of a mixture containing at least a substance having a catalytic action on a substance exhibiting properties and metal particles is fixed to a transparent substrate by a screen printing method It relates to solar cells.

  In the present invention, by arranging a bus bar on a flexible transparent substrate by a screen printing method, a counter electrode having excellent transparency, flexibility, and low surface resistance can be produced, and flexible dye increase having high conversion efficiency can be achieved. A solar cell can be produced.

Hereinafter, the present invention will be described in detail.
First, the counter electrode used in the present invention will be described. The counter electrode has a structure in which a bus bar made of a mixture containing at least a substance having a catalytic action on a substance exhibiting reversible electrochemical oxidation-reduction characteristics and metal particles is fixed on the transparent substrate surface by a screen printing method.
The transparent substrate used in the present invention is not particularly limited as long as it is flexible and transparent. For example, colorless or colored soda lime glass, Pyrex (registered trademark) glass, high transmittance glass called white plate, synthetic In addition to inorganic materials such as quartz, fused quartz, alumina, and zirconia, colorless or colored resins may be used. Specific examples of the resin include polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, and polymethylpentene. Is mentioned. In addition, the transparency in this invention is 10-100% of transmittance | permeability, Preferably it has the transmittance | permeability of 50% or more. Further, the flexible means has a thickness that can be easily deformed by stress, and the range of the thickness varies depending on the material, but the range of 5 μm to 0.5 mm, preferably 10 μm to 0.2 mm is desirable. .

In the present invention, it is essential to have a bus bar on the counter electrode substrate. The bus bar is formed by a screen printing method.
As materials used for the bus bar, substances having catalytic performance for redox oxidation or reduction and metal fine particles are essential components. Examples of the substance having catalytic performance include noble metals such as platinum, conductive organic compounds such as polydioxythiophene and polypyrrole, and carbon. The carbon capable of forming the catalyst layer is not particularly limited. For example, a diamond thin film doped with boron, graphite, graphite, glassy carbon, acetylene black, ketjen black, activated carbon, petroleum Examples include coke, fullerenes such as C60 and C70, and single-walled or multi-walled carbon nanotubes. The shape of the carbon material is not particularly limited as long as it finally forms a carbon layer, and the raw material shape may be any form such as powder, short fiber, long fiber, woven fabric, and non-woven fabric. Good.

  Examples of the material of the metal fine particles constituting the bus bar used in the present invention include tungsten, stainless steel, chromium, molybdenum, titanium, and platinum, and preferably tungsten, titanium, and platinum. The particle diameter of the metal fine particles is preferably in the range of 1 nm to 10 μm, more preferably in the range of 0.01 μm to 1 μm.

  In the present invention, the mixing ratio of the substance having catalytic performance to the metal fine particles (catalyst substance: metal fine particles (mass ratio)) is preferably in the range of 0.0005 to 0.1: 1, 0.001 to 0.05. A range of: 1 is more preferred. If the mixing ratio is too large, the conductivity is lowered, and if it is too small, the catalytic ability is lowered.

In the present invention, a paste is prepared by adding compounding materials such as various binders, dispersion materials, and solvents to the above-mentioned substance having catalytic performance and metal fine particles, and the paste is used for screen printing on a transparent substrate. And install.
As the paste compounding material, it is preferable to use various binders, dispersing agents, solvents and the like, and adjust the viscosity appropriately according to the installation method. As the binder, various polymers such as epoxy resins, known ceramics used in the semiconductor industry, glass components, and the like can be used. Examples of the paste containing these include silver glass conductive binder paste (DM3554 manufactured by DIEMAT, USA, NP-4731A, NP-4028A, NP-4734, NP-4736H, NP-4735, etc. manufactured by Noritake), thermosetting silver, and the like. Paste (DM6030HK manufactured by DIEMAT, USA, DM-351H-30 manufactured by Toyobo Co., Ltd.) and the like can be used, but other than those exemplified above, any material having a specific resistance of 20 μΩ · cm or less may be used. Is possible. The glass component used as the binder contains various metal oxides such as lead oxide, boron oxide, alumina, and titania in the component, but the component composition is not particularly limited.

A curable resin is also preferably used as the paste compounding material. The curable resin is not particularly limited, and various curing types such as a thermosetting type, a photocurable type, and an electron beam curable type can be applied as the curing method.
Specific examples of the curable resin include phenol resin, urea resin, epoxy resin, polyvinyl acetate, polyvinyl acetal, polyvinyl alcohol, polyacrylic and polymethacrylic acid ester, polycyanoacrylic acid ester, polyamide, and the like. .
In the case of thermosetting, those that can be cured at room temperature can be used, but when heating is required, heating can be performed using various ovens, infrared heaters, electric heaters, planar heating elements, and the like. Usually, it can be cured between room temperature and 150 ° C, preferably between room temperature and 100 ° C.
In the case of photocuring, any low-pressure, high-pressure, or ultrahigh-pressure mercury lamp, xenon lamp, incandescent lamp, laser light, or the like can be used as long as the lamp is adapted to the absorption wavelength of the initiator. During curing, the entire surface of the element may be exposed uniformly, and the entire surface may be cured at the same time, or it may be focused by moving a lamp or light source, guiding with a light guide material such as an optical fiber, or using a mirror or the like. Sequential curing may be performed by scanning with spot light.

  If the viscosity of the paste is too high, the paste cannot be sufficiently dropped onto the screen printing plate, and therefore printing with high accuracy cannot be performed. In this case, the printing plate cannot be printed with high accuracy. The viscosity adjustment of the paste depends on the kind and amount of the compounding material (binder), and the content of the binder is preferably in the range of 10:90 to 40:60, more preferably 15:85 by weight ratio to the metal fine particles. ~ 30: 70.

In the present invention, the bus bar made of the substance having the catalytic performance and the metal fine particles is disposed on the transparent substrate by the screen printing method. The bus bar width is preferably as narrow as possible because it limits the light incident area, and is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 0.5 mm or less.
The height of the bus bar is not particularly limited as long as the specific resistance can be 20 μΩ · cm or less. However, if the cell gap is too wide, the diffusion rate of electrons in the electrolytic solution is lowered, and therefore preferably 100 μm or less, more preferably 50 μm or less. More preferably, it is 20 μm or less.
The cross-sectional shape of the bus bar is not particularly limited, such as a circular shape, an oval shape, or a polygonal shape. However, from the stability of the bus bar, a cross-sectional shape such as a triangle, a quadrangle, or a trapezoid is preferable as shown in FIG.

As the shape of the bus bar, any shape can be adopted as long as the substrate resistance can be lowered. However, in order to increase the diffusion rate of the generated electrons, a continuous shape is preferable. Examples of the shape include a grid shape, a stripe shape, and a mesh shape. FIG. 2 shows an example of the shape of the bus bar.
As shown in FIG. 3, the ratio (Sb / Sa: coverage) of the bus bar region Sb (spotted portion in the figure) in the portion overlapping the active region Sa (semiconductor region) to the active region Sa is preferably 2. % To 30%, more preferably 4% to 20%, still more preferably 5% to 15%.
Further, the bus bar may be installed in a plurality of times in order to obtain a predetermined performance at the time of installation, or may be installed using two or more kinds of the materials.

Next, a metal foil electrode having a semiconductor layer modified with a sensitizer will be described.
First, the metal foil used in the present invention is not particularly limited as long as it is flexible. Examples of the material include titanium, chromium, tungsten, molybdenum, platinum, tantalum, niobium, zirconium, zinc, various stainless steels, and alloys thereof. Preferably, titanium, chromium, tungsten, various stainless steels and alloys thereof are desirable. The thickness of the metal foil is not particularly limited as long as it is flexible, and varies depending on the material, but is, for example, in the range of 5 μm to 0.5 mm, preferably 20 μm to 0.2 mm.

No particular limitation is imposed on the semiconductor layer used in the present invention, for _{example, Bi 2 S 3, CdS,} CdSe, CdTe, CuInS 2, CuInSe 2, Fe 2 O 3, GaP, GaAs, InP, Nb 2 O 5, PbS , Si, SnO ₂ , TiO ₂ , WO ₃ , ZnO, ZnS and the like, preferably CdS, CdSe, CuInS ₂ , CuInSe ₂ , Fe ₂ O ₃ , GaAs, InP, Nb ₂ O ₅ , PbS, SnO _2. , TiO ₂ , WO ₃ , ZnO, or a plurality of combinations. Particularly preferred are TiO ₂ , ZnO, SnO ₂ , Nb ₂ O ₅ and combinations thereof, and most preferred are TiO ₂ , ZnO, SnO ₂ and combinations thereof.
The semiconductor used in the present invention may be single crystal or polycrystalline. As the crystal system, for example, in the case of titanium oxide, anatase type, rutile type, brookite type and the like are mainly used, but anatase type is preferable.

  The thickness of the semiconductor layer is arbitrary, but is usually 0.05 μm or more and 100 μm or less, preferably 0.5 μm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less.

  The semiconductor layer can be formed by applying the semiconductor nanoparticle dispersion, sol solution, or the like on the metal foil by a known method. The coating method in this case is not particularly limited, and examples include a method of obtaining a thin film by a casting method, a spin coating method, a dip coating method, a bar coating method, and various printing methods including a screen printing method. it can. Moreover, it can also form on the said metal foil by a vacuum evaporation method, an ion plating method, CVD or sputtering method using the said semiconductor material or its precursor material. Further, it can be formed by anodic oxidation of a metal material used as a precursor of the semiconductor layer. Here, the anodic oxidation is a metal material that is a precursor of the semiconductor layer in the electrolyte, for example, a metal selected from titanium, niobium, tantalum, zirconium and alloys containing them as an anode, and an arbitrary metal as a cathode. This is a technique for forming an oxide on the surface of the metal on the anode side by applying an electric field, and it is sufficient that the state that these metals are anodes during the anodic oxidation treatment, and the anodes and cathodes are alternated. This includes the case where it is implemented.

  As the metal material used for anodization, titanium or an alloy containing titanium (hereinafter referred to as a titanium alloy) is most preferable. The titanium or titanium alloy used in the present invention can be industrial pure titanium prepared with oxygen, iron, nitrogen, or hydrogen, or a low alloy titanium alloy having a certain degree of press formability. 2 types, 3 types, 4 types of industrial pure titanium, alloys with improved corrosion resistance by adding nickel, ruthenium, tantalum, palladium, etc., aluminum, vanadium, molybdenum, tin, iron, chromium, niobium, etc. One example is an added alloy. In the present invention, the titanium alloy means an alloy containing 50% or more of titanium.

  Regarding the shape, in addition to various shapes such as titanium or titanium alloy plate, rod, mesh, etc., titanium or titanium alloy was grown as a film on the surface of different conductive materials such as plate, rod, mesh, etc. Examples thereof include, but are not limited to, semiconductors having a shape such as an object, a plate, a rod, and a mesh, or a material in which titanium or a titanium alloy is grown as a film on the surface of an insulating material. Regarding the surface smoothness, in the anodizing step, it is possible to grow titania even if the surface structure has a complicated shape, and the smoothness is not limited.

Examples of the electrolyte solution used for anodization include phosphoric acid, sulfuric acid or a mixed acid thereof, an aqueous solution in which glycerophosphate and metal acetate are dissolved, or an electrolyte solution containing ions containing halogen atoms.
In particular, in the present invention, it is preferable to use an electrolyte solution containing ions containing halogen atoms. By using such an electrolytic solution, a semiconductor layer made of titania having a tube shape with a high aspect ratio can be obtained. The ion containing a halogen atom here is an ion containing any atom of fluorine, chlorine, bromine and iodine, specifically, fluoride ion, chloride ion, bromide ion, iodide ion, Perchlorate ion, perbromate ion, periodate ion, chlorate ion, bromate ion, iodate ion, chlorite ion, bromite ion, hypochlorite ion, hypobromite ion, next Examples include iodate ion. These ions may be used alone or as a mixture of two or more.

Specifically, as the electrolyte solution containing these ions, an aqueous solution of an acid or salt that forms these ions is used. The concentration of the acid or salt is preferably 0.001 to 50% by volume, more preferably 0.005 to 10% by volume, and still more preferably 0.01 to 5% by volume.
As such an electrolyte solution containing a halogen atom, a perchloric acid aqueous solution is particularly suitable.

The electrolyte solution may contain a water-soluble titanium compound. Since a water-soluble titanium compound is generally hydrolyzed in an aqueous solution to produce titania, by including this, titania is further produced by hydrolysis on the surface of titania produced by anodization. It is possible to prevent the redissolution of titania in the electrolyte solution and increase the titania aspect ratio.
Examples of such water-soluble titanium compounds include titanium alkoxides such as titanium isopropoxide, titanium trichloride, titanium tetrachloride, titanium fluoride, ammonium tetrafluorotitanate, titanium sulfate, and titanyl sulfate. Is not to be done. The concentration is preferably 0.001 to 1000, more preferably 0.01 to 50, and still more preferably 0.04 to 5 in terms of molar ratio to the halogen atom-containing ions.

Further, the electrolyte solution may contain an acidic compound different from the acid or salt that forms ions containing halogen atoms. By containing an acidic compound, the reaction rate such as promoting or suppressing the anodic oxidation rate can be controlled.
Examples of such acidic compounds include sulfuric acid, nitric acid, acetic acid, hydrogen peroxide, oxalic acid, phosphoric acid, chromic acid, glycerophosphoric acid and the like in addition to the above-mentioned halide or acid of its oxidant ion. Is not to be done. The concentration is preferably 0.001 to 1000, more preferably 0.01 to 50, and still more preferably 0.04 to 5 in terms of molar ratio to the halogen atom-containing ions.

The electrolyte solution may contain titania fine particles. By containing titania fine particles, the produced titania can be prevented from redissolving in the electrolyte solution, and the titania aspect ratio can be increased.
Such titania fine particles preferably have a particle size of 0.5 to 100 nm, more preferably 2 to 30 nm. Specific examples include those prepared from titanium ore by a liquid phase method and those synthesized by a vapor phase method, a sol-gel method, and a liquid phase growth method. Here, the gas phase method is a method for producing titania by baking hydrous titanium oxide obtained by heating and hydrolyzing titanium ore with a strong acid such as sulfuric acid at 800 ° C. to 850 ° C. The liquid phase method is a method for producing titania by bringing oxygen and hydrogen into contact with titanium chloride. In the sol-gel method, titanium alkoxide is hydrolyzed in an alcohol aqueous solution to form a sol, and further, a hydrolysis catalyst is added to the sol, left to gel, and the gelled product is baked to titania. It is a method of manufacturing. The liquid phase growth method is a method for obtaining titania by hydrolysis of titanium fluoride, ammonium tetrafluorotitanate, titanyl sulfate or the like.

Anodization is usually performed at an applied voltage of 5 to 200 V, preferably 10 to 100 V, and a current density of 0.2 to 500 mA / cm ² , preferably 0.5 to 100 mA / cm ² for 1 minute to 24 hours. , Preferably 5 minutes to 10 hours. At this time, the applied voltage and current density can be changed in a pulse manner. Although it does not specifically limit as a period of the pulse in this case, 0.001 Hz-1 MHz, Preferably it is 0.01 Hz-10000 Hz, More preferably, 0.1 Hz-1000 Hz is mentioned. The amplitude of the pulse is not particularly limited as long as it is within the range of the applied voltage and current density described above, and examples thereof include ON-OFF type pulses and anode-cathode inverted type pulses.
Moreover, 0-50 degreeC is preferable and, as for the temperature of the electrolyte aqueous solution at the time of anodizing, More preferably, it is 0-40 degreeC.

By the above method, a titanium metal or a titanium alloy can be anodized to obtain a semiconductor layer composed of nanotube-shaped titania having a high aspect ratio. The aspect ratio is a ratio of length to diameter, and is composed of nanotube-shaped titania having an aspect ratio of 6 or more, preferably 10 or more, more preferably 20 or more, and further preferably 30 or more by using the method of the present invention. A semiconductor layer can be obtained.
The diameter of the nanotube-shaped titania obtained by the above method is usually 5 nm to 500 nm, preferably 10 nm to 300 nm, although it varies depending on the production conditions. The length also varies depending on the production conditions and the like, but is usually 0.1 μm to 100 μm, preferably 1 μm to 50 μm.

  Further, the above-described semiconductor nanoparticle dispersion, sol solution, or the like may be further applied to the semiconductor layer produced by the above-described anodic oxidation method by a known method.

  If necessary, the semiconductor layer formed by the above method can be subjected to post-treatment such as heat treatment, water vapor treatment, ultraviolet irradiation, and microwave irradiation. Thereby, in the case of titania, for example, its crystal structure (anatase, rutile, brookite, and mixed crystals thereof) can be grown. For example, in the case of heat treatment, the crystallinity of titania is improved by performing the treatment at a temperature of 100 ° C. to 1200 ° C. for 10 minutes to 500 minutes, preferably at a temperature of 300 ° C. to 800 ° C. for 30 minutes to 160 minutes. I can expect that. With these treatments, the tube shape does not collapse.

Next, the sensitizer for modifying (adsorbing, adhering, etc.) the semiconductor layer in the present invention will be described.
Examples of the sensitizer include dyes such as metal complex dyes, organic dyes, and natural dyes. Those having a functional group such as carboxyl group, hydroxyl group, sulfonyl group, phosphonyl group, carboxylalkyl group, hydroxyalkyl group, sulfonylalkyl group, phosphonylalkyl group in the molecule of the dye are preferably used.

As the metal complex dye, a complex of ruthenium, osmium, iron, cobalt, zinc, mercury (for example, mellicle chrome), metal phthalocyanine, chlorophyll, or the like can be used.
Examples of the metal complex dye used in the present invention are as follows.

(Dye 1)

Here, X ₁ represents a monovalent anion, but each X ₁ may be independent or cross-linked. For example, the following is exemplified.

(Dye 2)

Here, X ₁ is the same as X ₁ described above. X ₂ represents a monovalent anion, and examples thereof include the following.

Y is a monovalent anion, which is a halogen ion, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) _{2 ^{N -, PF 6 -, AsF}} 6 -, CH 3 COO -, CH 3 (C 6 H 4) SO 3 -, and _{(C 2 F 5 SO 2)} 3 C - , and the like.

(Dye 3)

Here, Z is an atomic group having an unshared electron pair, and two Zs may be independent or bridged. For example, the following is exemplified.

Y is a monovalent anion, which is a halogen ion, SCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) _{2 ^{N -, PF 6 -, AsF}} 6 -, CH 3 COO -, CH 3 (C 6 H 4) SO 3 -, and _{(C 2 F 5 SO 2)} 3 C - , and the like.

(Dye 4)

  Examples of organic dyes include, but are not limited to, cyanine dyes, hemicyanine dyes, merocyanine dyes, xanthene dyes, triphenylmethane dyes, metal-free phthalocyanine dyes, and the like. Examples of the organic dye used in the present invention are as follows.

As a semiconductor that can be used as a dye, an amorphous semiconductor having a large i-type light absorption coefficient, a direct transition semiconductor, or a fine particle semiconductor that exhibits a quantum size effect and efficiently absorbs visible light is preferable.
Moreover, in order to make the wavelength range of photoelectric conversion as wide as possible and increase the conversion efficiency, it is possible to mix one or more of the various semiconductors, metal complex dyes and organic dyes described above. Moreover, the sensitizer to mix and its ratio can be selected so that it may match the wavelength range and intensity distribution of the target light source.

  As a method of attaching the sensitizer to the semiconductor layer, a solution in which the sensitizer is dissolved in a solvent is applied by spray coating or spin coating on the semiconductor layer and then dried. it can. In this case, the substrate may be heated to an appropriate temperature. Alternatively, a method in which a semiconductor layer is immersed in a solution and adsorbed can be used. The immersion time is not particularly limited as long as the dye is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, particularly preferably 10 minutes to 20 hours. Moreover, you may heat a solvent and a board | substrate when immersing as needed. The concentration of the dye in the case of a solution is preferably about 1 to 1000 mmol / L, preferably about 10 to 500 mmol / L.

  The solvent to be used is not particularly limited, but water and an organic solvent are preferably used. Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol, acetonitrile, propionitrile, methoxypropionitrile, and glutaronitrile. Nitrile solvents, benzene, toluene, o-xylene, m-xylene, p-xylene, pentane, heptane, hexane, cyclohexane, heptane, acetone, methyl ethyl ketone, diethyl ketone, 2-butanone and other ketones, diethyl ether, tetrahydrofuran, ethylene Carbonate, propylene carbonate, nitromethane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfo Phorane, dimethoxyethane, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethyl sulfoxide, dioxolane, sulfolane, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, ethyldimethyl phosphate, tributyl phosphate, tripentyl phosphate, phosphorus Trihexyl acid, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, tris phosphate (trifluoromethyl), tris phosphate (pentafluoroethyl), triphenyl polyethylene glycol, polyethylene glycol, etc. It can be used.

Next, the electrolyte used in the present invention will be described.
The electrolyte is required to contain a substance exhibiting reversible electrochemical redox characteristics, and may be either a liquid system or a solid system.
Further, the ionic conductivity of the electrolyte is usually 1 × 10 ⁻⁷ S / cm or more at room temperature, preferably 1 × 10 ⁻⁶ S / cm or more, more preferably 1 × 10 ⁻⁵ S / cm or more. desirable. The ionic conductivity can be obtained by a general method such as a complex impedance method.

In the electrolyte of the present invention, the diffusion coefficient of an oxidant of a substance that exhibits reversible electrochemical redox characteristics is 1 × 10 ⁻⁹ cm ² / s or more, preferably 1 × 10 ⁻⁸ cm ² / s. As described above, more preferably 1 × 10 ⁻⁷ cm ² / s or more is desirable. The diffusion coefficient is an index indicating ion conductivity, and can be obtained by a general method such as constant potential current characteristic measurement or cyclic voltammogram measurement.

  The thickness of the electrolyte layer is not particularly limited, but is preferably 1 μm or more, more preferably 10 μm or more, and preferably 3 mm or less, more preferably 1 mm or less.

  The liquid electrolyte is not particularly limited. Usually, a solvent, a substance exhibiting reversible electrochemical redox characteristics (soluble in a solvent), and, if necessary, a supporting electrolyte as a basic component Composed. In addition to these, other optional components such as an ultraviolet absorber and an amine compound may be further contained as desired.

  Any solvent can be used as long as it is generally used in electrochemical cells and batteries. Specifically, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, 3-methyl-2-oxazolidinone, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, ethylene carbonate, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, 3-methylsulfolane, dimethoxyethane, propiononitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, dimethylacetamide, methylpyrrolidinone, dioxolane, trimethyl phosphate, triethyl phosphate, Tripropyl phosphate, ethyl dimethyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, trihexyl phosphate Ptyl, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, tris phosphate (trifluoromethyl), tris phosphate (pentafluoroethyl), triphenyl polyethylene glycol phosphate, polyethylene glycol, and the like can be used. In particular, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, 3-methyl-2-oxazolidinone, γ-butyrolactone, sulfolane, 3-methylsulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, dimethylacetamide, methylpyrrolidinone, trimethyl phosphate and triethyl phosphate are preferred. Also, room temperature molten salts can be used. Here, the room temperature molten salt is a salt composed of an ion pair that is melted at room temperature (that is, in a liquid state) and usually has a melting point of 20 ° C. or lower and is a liquid at a temperature exceeding 20 ° C. Is a salt.

Examples of the room temperature molten salt include the following.

Here, R represents an alkyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and X ⁻ represents a halogen ion, SCN ⁻ , SeCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , dicyandiamide ion, tricyanomethane ion or thiocyanate.

Here, R ¹ and R ² are each an alkyl group having 1 to 10 carbon atoms (preferably a methyl group or an ethyl group), or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms (preferably a benzyl group). It may be the same or different. X ⁻ represents a halogen ion, SCN ⁻ , SeCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , dicyandiamide ion, tricyanomethane ion or thiocyanate are shown.

Here, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 or more carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms (such as a phenyl group), or methoxymethyl. Represents a group or the like, which may be the same or different. X ⁻ represents a halogen ion, SCN ⁻ , SeCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , dicyandiamide ion, tricyanomethane ion or thiocyanate ion are shown.

  One of these solvents may be used alone, or two or more thereof may be mixed and used.

In addition, the substance exhibiting reversible electrochemical redox characteristics is usually referred to as a so-called redox material, but the type is not particularly limited. Examples of such substances include ferrocene, p-benzoquinone, 7,7,8,8-tetracyanoquinodimethane, N, N, N ′, N′-tetramethyl-p-phenylenediamine, tetrathiafulvalene, thi Examples thereof include complex salts such as anthracene, p-toluylamine, ferrocyanic acid-ferricyanate, sodium polysulfide, alkylthiol-alkyldisulfide, hydroquinone-quinone, and viologen dye. Further, salts having a counter anion (X ⁻ ) selected from halogen ions, SCN ⁻ and SeCN ⁻ are also preferably used. Examples of salts having these anions include alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts, and guanidinium salts. Specific examples of the alkali metal salt and alkaline earth metal salt include LiX, NaX, KX, CeX, MgX ₂ , and CaX ₂ .

Specific examples of the quaternary ammonium salt include (CH ₃ ) ₄ N ⁺ X ⁻ , (C ₂ H ₅ ) ₄ N ⁺ X ⁻ , (nC ₄ H ₉ ) ₄ N ⁺ X ⁻ , Moreover,

等が挙げられる。

Etc.

等が挙げられる。 Specific examples of the quaternary phosphonium salt include (CH ₃ ) ₄ P ⁺ X ⁻ , (C ₂ H ₅ ) ₄ P ⁺ X ⁻ , (C ₃ H ₇ ) ₄ P ⁺ X ⁻ , (C ₄ H ₉ ) ₄ P ⁺ X ⁻ ,

Etc.

Examples of the imidazolium salt include those represented by the following general formula.

Here, R ¹ and R ² each represent an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms, and may be the same or different. R ^{3 to} R ⁵ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms, and may be the same or different. X ⁻ represents a halogen ion, SCN ⁻ or SeCN ⁻ .

  Specific examples of such imidazolium salts include 1-propyl-2,3-dimethyl-imidazolium salt, 1-propyl-3-methylimidazolium salt, 1-ethyl-3-methylimidazolium salt, Examples include hexyl-3-methylimidazolium salt.

  Specific examples of the guanidinium salt include guanidinium hydrochloride, guanidinium thiocyanate, and guanidinium nitrate.

  Of course, a mixture of these can also be used suitably.

In addition, redox room temperature molten salts can also be used as substances exhibiting reversible electrochemical redox properties. Here, the redox room temperature molten salt is a salt composed of an ion pair melted at room temperature (that is, in a liquid state), and usually has a melting point of 20 ° C. or lower and is a liquid at a temperature exceeding 20 ° C. A salt consisting of a pair is shown, and a reversible electrochemical redox reaction can be performed. When redox room temperature molten salts are used as the substance exhibiting reversible electrochemical redox properties, the solvent may be used or may not be used.
The redox room temperature molten salt can be used alone or in combination of two or more.
Examples of the redox ordinary-temperature molten salt, for example, of the room temperature molten salt as described above, X ^- halogen ions, SCN ^- or SeCN ^- include those of.

As the redox material, only one of the oxidized form and the reduced form may be used, or the oxidized form and the reduced form may be mixed at an appropriate molar ratio and added. Further, these redox pairs may be added so as to show electrochemical responsiveness. Materials exhibiting such properties include halogen ions, SCN ⁻ , SeCN ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and (C ₂ F ₅ SO _2. ) Ferrocenium having a counter anion selected from ₂ N ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , and (C ₂ F ₅ SO ₂ ) ₃ C ⁻ In addition to metallocenium salts such as, halogens such as iodine, bromine, and chlorine can also be used.

  The amount of the substance exhibiting reversible electrochemical oxidation-reduction characteristics is not particularly limited as long as it does not cause defects such as precipitation in the electrolyte. However, the concentration in the electrolyte is usually 0.001 to 10 mol / L, preferably 0.01 to 1 mol / L. However, this is not the case when redox room temperature molten salts are used alone.

  Further, as the supporting electrolyte added as necessary, salts, acids, alkalis, and room temperature molten salts that are usually used in the field of electrochemistry or the field of batteries can be used.

  The salt is not particularly limited, and examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, quaternary phosphonium salts, cyclic quaternary phosphonium salts, and imidazolium. Salts, guanidinium salts and the like can be used.

Specific examples of the salts include ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , PF ₆ ⁻ and AsF ₆ ^−. , CH ₃ COO ⁻ , CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₃ C ⁻ , and an alkali metal salt having a counter anion selected from dicyandiamide ion (DCA ⁻ ), alkaline earth Examples thereof include metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, quaternary phosphonium salts, cyclic quaternary phosphonium salts, imidazolium salts, and guanidinium salts.

Specific examples of the alkali metal and alkaline earth metal salts include LiClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, _{CH 3 COOLi, CH 3 (C} 6 H 4) SO 3 Li, Li (C 2 F 5 SO 2) 3 C, LiDCA, Mg (ClO 4) 2, Mg (BF 4) 2, Mg (PF 6) 2 Mg (CF ₃ SO ₃ ) ₂ , Mg [(CF ₃ SO ₂ ) ₂ N] ₂ , Mg [(C ₂ F ₅ SO ₂ ) ₂ N] ₂ , Mg (CH ₃ COO) ₂ , Mg [CH ₃ (C ₆ H ₄ ) SO ₃ ] ₂ , Mg [(C ₂ F ₅ SO ₂ ) ₃ C] ₂ , Mg (DCA) _{2 and the} like.

Specific examples of the quaternary ammonium salt and the cyclic quaternary ammonium salt include (CH ₃ ) ₄ N ⁺ BF ₄ ⁻ , (C ₂ H ₅ ) ₄ N ⁺ BF ₄ ⁻ , and (n—C ₄ H ₉ ) ₄ N. ^{_{+ BF 4 -, (C 2}} H 5) 4 n + Br -, (C 2 H 5) 4 n + ClO 4 -, (n-C 4 H 9) 4 n + ClO 4 -, CH 3 (C 2 H ₅ ) ₃ N ⁺ BF ₄ ⁻ , (CH ₃ ) ₂ (C ₂ H ₅ ) ₂ N ⁺ BF ₄ ⁻ , (CH ₃ ) ₄ N ⁺ SO ₃ CF ₃ ⁻ , (C ₂ H ₅ ) ₄ N ⁺ SO ₃ CF ₃ ⁻ , (nC ₄ H ₉ ) ₄ NSO ₃ CF ₃ ⁻ ,

等が挙げられる。

Etc.

Specific examples of the quaternary phosphonium salt and the cyclic quaternary phosphonium salt include (CH ₃ ) ₄ P ⁺ BF ₄ ⁻ , (C ₂ H ₅ ) ₄ P ⁺ BF ₄ ⁻ , (C ₃ H ₇ ) ₄ P ^+. BF ₄ ⁻ , (C ₄ H ₉ ) ₄ P ⁺ BF ₄ ⁻ ,

等が挙げられる。

Etc.

  Specific examples of imidazolium salts include 1-propyl-2,3-dimethyl-imidazolium tetrafluoroborate, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetra Examples thereof include fluoroborate and 1-hexyl-3-methylimidazolium tetrafluoroborate.

  Specific examples of the guanidinium salt include guanidinium hydrochloride, guanidinium thiocyanate, and guanidinium nitrate.

  Moreover, these mixtures can also be used suitably.

The acids are not particularly limited, and inorganic acids and organic acids can be used. Specifically, sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, carboxylic acids and the like can be used.
The alkalis are not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used.
As the room temperature molten salts, the aforementioned compounds are used.

  There is no restriction | limiting in particular about the usage-amount of the above supporting electrolyte, Usually, it is 0.01-10 mol / L as a density | concentration in electrolyte, Preferably it is made to contain about 0.05-1 mol / L. it can.

Next, optional components to be added as desired will be described.
Examples of optional components include ultraviolet absorbers and amine compounds. Although it does not specifically limit as a ultraviolet absorber which can be used, Organic UV absorbers, such as a compound which has a benzotriazole skeleton and a compound which has a benzophenone skeleton, are mentioned as a typical thing.

As the compound having a benzotriazole skeleton, for example, a compound represented by the following general formula (1) is preferably exemplified.

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. The substitution position of R ¹ is the 4-position or 5-position of the benzotriazole skeleton, but the halogen atom and the alkyl group are usually located at the 4-position. R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. R ³ represents an alkylene group or alkylidene group having 1 to 10 carbon atoms, preferably 1 to ³ carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.

  Specific examples of the compound represented by the general formula (1) include 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid. 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzeneethanoic acid, 3- (2H-benzotriazol-2-yl) -4-hydroxybenzene Ethanoic acid, 3- (5-methyl-2H-benzotriazol-2-yl) -5- (1-methylethyl) -4-hydroxybenzenepropanoic acid, 2- (2′-hydroxy-5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 '-Di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 3- (5-chloro-2H-benzo And triazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester.

Suitable examples of the compound having a benzophenone skeleton include compounds represented by the following general formulas (2) to (4).

In the general formulas (2) to (4), R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² are the same or different from each other, and are a hydroxyl group, 1 to 10 carbon atoms, Preferably 1-6 alkyl groups or alkoxy groups are shown. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group.
R ⁴ , R ⁷ and R ¹⁰ represent an alkylene group or alkylidene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Examples of the alkylidene group include an ethylidene group and a propylidene group.
p ₁ , p ₂ , p ₃ , q ₁ , q ₂ , and q ₃ each independently represent an integer of 0 to 3.

Preferred examples of the compound having a benzophenone skeleton represented by the general formulas (2) to (4) include 2-hydroxy-4-methoxybenzophenone-5-carboxylic acid and 2,2′-dihydroxy-4-methoxybenzophenone. -5-carboxylic acid, 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy -2'-carboxybenzophenone and the like.
Of course, two or more of these can be used in combination.

  The use of the UV absorber is optional, and the amount used is not particularly limited. However, when used, the concentration in the electrolyte is 0.001 to 10 mol / L, preferably 0. It is desirable that it is 01-1 mol / L.

  Moreover, it does not specifically limit as an amine compound which can be contained in the electrolyte of this invention, Various aliphatic amines, aromatic amines, etc. can be used. For example, pyridine derivatives, aniline derivatives, quinoline derivatives, imidazole derivatives, and the like are typical examples. By adding these amine compounds, an improvement in open circuit voltage is expected. Specific examples of these compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-t-butyl-pyridine, 4-dimethylaminopyridine, 2-dimethylaminopyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 4-pyridinopyridine, 4-pyrrolidinopyridine, 4- (2-aminoethyl) pyridine, 2- (2-amino Ethyl) pyridine, 2-methoxymethylpyridine, picolinic acid, 2-pyridinemethanol, 2-pyridineethanol, 3-pyridinemethanol, 2,3-cyclopentenopyridine, nicotinamide, nicotinic acid, 4,4′-bipyridine, Pyridine derivatives such as 2,2'-bipyridine, and anilines such as aniline and dimethylaniline Phosphorus derivatives, quinoline, quinoline derivatives such as isoquinoline, benzimidazole, imidazole derivatives such as N- methyl benzimidazole.

  The use of the amine compound is optional, and the amount used is not particularly limited, but when used, the concentration in the electrolyte is 0.001 to 10 mol / L, preferably 0.01. It is desirable that it is ˜1 mol / L.

  The electrolyte used in the present invention may be a liquid as described above, but a polymer solid electrolyte is particularly preferable from the viewpoint that solidification is possible. As the polymer solid electrolyte, it is particularly preferable that (a) the polymer matrix (component (a)) contains at least (b) a substance (component (b)) exhibiting reversible electrochemical redox characteristics. If desired, those further containing (c) a plasticizer (component (c)) may be mentioned. In addition to these, other optional components such as the above-described supporting electrolyte, ultraviolet absorber, and amine compound may be further contained as desired. As the polymer solid electrolyte, the component (b), the component (b) and the component (c), or a further optional component is held in a polymer matrix to form a solid state or a gel state.

  In the present invention, the material that can be used as the polymer matrix (component (a)) is a polymer matrix alone, solid state or gel by adding a plasticizer, adding a supporting electrolyte, or adding a plasticizer and a supporting electrolyte. There is no particular limitation as long as the state is formed, and generally used so-called polymer compounds can be used.

  Examples of the polymer compound exhibiting characteristics as the polymer matrix include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl Examples thereof include polymer compounds obtained by polymerizing or copolymerizing monomers such as acrylate, ethyl acrylate, methyl methacrylate, styrene, and vinylidene fluoride. These polymer compounds may be used alone or in combination. Among these, a polyvinylidene fluoride polymer compound is particularly preferable.

  Examples of the polyvinylidene fluoride polymer compound include a homopolymer of vinylidene fluoride, or a copolymer of vinylidene fluoride and another polymerizable monomer, preferably a radical polymerizable monomer. Specific examples of other polymerizable monomers copolymerized with vinylidene fluoride (hereinafter referred to as copolymerizable monomers) include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride. Acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene and the like can be exemplified. Among these, a copolymer with a monomer having a carboxyl group is particularly preferable. That is, as the polyvinylidene fluoride polymer compound, those containing a carboxyl group are preferable.

  These copolymerizable monomers can be used in the range of 0.1 to 50 mol%, preferably 1 to 25 mol%, based on the total amount of monomers.

  As the copolymerizable monomer, hexafluoropropylene is preferably used. In the present invention, in particular, it can be preferably used as an ion conductive film using a vinylidene fluoride-hexafluoropropylene copolymer obtained by copolymerizing 1-25 mol% of hexafluoropropylene with vinylidene fluoride as a polymer matrix. Two or more kinds of vinylidene fluoride-hexafluoropropylene copolymers having different copolymerization ratios may be mixed and used.

  Further, two or more of these copolymerizable monomers can be used for copolymerization with vinylidene fluoride. For example, vinylidene fluoride + hexafluoropropylene + tetrafluoroethylene, vinylidene fluoride + hexafluoropropylene + acrylic acid, vinylidene fluoride + hexafluoropropylene + maleic anhydride, vinylidene fluoride + tetrafluoroethylene + ethylene, vinylidene fluoride A copolymer obtained by copolymerization with a combination of + tetrafluoroethylene + propylene can also be used.

  Furthermore, in the present invention, a polyacrylic acid-based polymer compound, a polyacrylate-based polymer compound, a polymethacrylic acid-based polymer compound, a polymethacrylate-based polymer compound, One or more polymer compounds selected from acrylonitrile polymer compounds and polyether polymer compounds may be used in combination. Alternatively, one or more kinds of copolymers obtained by copolymerizing two or more kinds of monomers of the above-described polymer compound with a polyvinylidene fluoride polymer compound may be used. In this case, the blending ratio of the homopolymer or copolymer is usually preferably 200 parts by mass or less with respect to 100 parts by mass of the polyvinylidene fluoride polymer compound.

  The weight average molecular weight of the polyvinylidene fluoride polymer compound used in the present invention is usually 10,000 to 2,000,000, preferably 100,000 to 1,000,000. can do.

As the substance (component (b)) exhibiting reversible electrochemical oxidation-reduction characteristics, specifically, various redox materials and redox room temperature molten salts exemplified in the above-described liquid electrolyte are used.
When components other than redox room temperature molten salts are used as component (b), it is usually preferred to use in combination with component (c). When redox room temperature molten salts are used as the component (b), the component (c) may or may not be used in combination.

The amount of the substance exhibiting reversible electrochemical oxidation-reduction characteristics (component (b)) is not particularly limited, but is usually 0.1% by mass or more, preferably 1% by mass or more in the polymer solid electrolyte. More preferably, it is 10% by mass or more and 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less.
In addition, it is preferable to use a component (b) together with a plasticizer (component (c)).

The plasticizer (component (c)) acts as a solvent for substances exhibiting reversible electrochemical redox properties. Any plasticizer can be used as long as it can be generally used as an electrolyte solvent in an electrochemical cell or battery, and specific examples thereof include various solvents exemplified in liquid electrolytes. In particular, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetonitrile, 3-methyl-2-oxazolidinone, γ-butyrolactone, sulfolane, 3-methylsulfolane, dioxolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, dimethylacetamide, methylpyrrolidinone, trimethyl phosphate and triethyl phosphate are preferred. Moreover, the above-mentioned room temperature molten salts can also be used.
One plasticizer may be used alone, or two or more plasticizers may be mixed and used.

  The amount of the plasticizer (component (c)) used is not particularly limited, but is usually 20% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and 98% by mass in the polymer solid electrolyte. It can be contained in an amount of not more than mass%, preferably not more than 95 mass%, more preferably not more than 90 mass%.

When the component (b) and the component (c) are used in combination, it is desirable that the component (b) has a mixing ratio that dissolves in the component (c) and does not cause precipitation even when the polymer solid electrolyte is formed. Preferably component (b) / component (c) is 0.01-0.5 by mass ratio, More preferably, it is the range of 0.03-0.3.
For component (a), the mass ratio of component (a) / (component (b) + component (c)) is preferably 1/20 to 1/1, more preferably 1/10 to 1/2. It is desirable to be in the range.

In addition to these, the solid electrolyte may further contain other optional components such as a supporting electrolyte, an ultraviolet absorber, and an amine compound as desired.
The amount of the supporting electrolyte used in the polymer solid electrolyte is not particularly limited and is arbitrary, but is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more in the polymer solid electrolyte. And 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less. In addition, the types and contents of ultraviolet absorbers, amine compounds and the like are as exemplified in the liquid electrolyte.

  In the present invention, the polymer solid electrolyte can be used as an ion conductive film. For example, an ion conductive film can be obtained by forming a polymer solid electrolyte comprising the components (a) and (b) or an optional component further blended as desired into a film by a known method. The molding method in this case is not particularly limited, and examples thereof include a method of obtaining in a film state by extrusion molding and a casting method, a spin coating method, a dip coating method, an injection method, and an impregnation method.

Extrusion molding can be performed by a conventional method, and after the mixture is melted by heating, film molding is performed.
Regarding the casting method, the mixture can be formed into a film by further adjusting the viscosity with an appropriate diluent, applying the mixture with a normal coater used in the casting method, and drying. As the coater, a doctor coater, a blade coater, a rod coater, a knife coater, a reverse roll coater, a gravure coater, a spray coater, and a curtain coater can be used, and they can be selectively used depending on the viscosity and the film thickness.
As for the spin coating method, the mixture can be formed into a film by further adjusting the viscosity with an appropriate diluent, applying the mixture with a commercially available spin coater, and drying.
As for the dip coating method, a film can be formed by adjusting the viscosity of the mixture with an appropriate diluent to prepare a mixture solution, pulling up an appropriate base from the mixture solution, and drying.

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

Example 1
(1) Production of dye-adsorbing titania electrode A titanium foil (purity: 99.7% by weight) having a size of 10 cm × 10 cm and a thickness of 0.05 mm was prepared and subjected to ultrasonic cleaning in ethanol for 5 minutes. One side of this titanium foil is coated with titania paste (Ti-Nanoxide-T / SP, manufactured by Solaronics) using an applicator with a gap of 180 μm, dried, and baked at 520 ° C. for 1 hour to oxidize 18 μm in thickness. A titanium layer was formed. Next, the titanium oxide electrode is immersed in an aqueous solution obtained by diluting a titanium tetrachloride aqueous solution (16.5% product, manufactured by Sumitomo Titanium Co., Ltd.) 25 times, and left in a sealed state at 40 ° C. for 40 minutes. And dried at 450 ° C. for 1 hour.
The titania electrode obtained above was immersed in a ruthenium dye (Rutenium 535-bisTBA: Solaronics) / ethanol solution (4.0 × 10 ⁻⁴ mol / L) for 15 hours, washed with ethanol, and dye-adsorbed titania. An electrode was produced.

(2) Fabrication of counter electrode A paste containing titanium fine powder, graphite, and thermosetting paste in a weight ratio of 10: 0.01: 4 on a polyphenylene sulfide substrate by a screen printing method with a line width of 25 μm and the center of the line Bus bar printing was performed at equal intervals so that the distance between them was 150 μm. Thereafter, heat treatment was performed at 100 ° C. for 1 hour and 30 minutes. The coverage of the bus bar was 16.7%.

(3) Production of photoelectric conversion element After part of the titania on the periphery of the titania electrode was scraped off, a 1.5 mmφ injection hole for injecting electrolyte was formed in one corner. A butyl rubber seal was placed around the substrate, and glass beads having a diameter of 53 to 63 μm were dispersed on the side of the butyl rubber. On top of this, the bus bar surface of the counter electrode produced above was put together and adhered by applying a pressure of 2 MPa. Using the injection hole of the obtained cell, 0.1 mol / L lithium iodide, 0.5 mol / L 1-propyl-2,3-dimethyl-imidazolium iodide, 0.05 mol / L iodine, A 3-methoxypropionitrile solution containing 0.5 mol / L of 4-t-butylpyridine is vacuum-injected, the injection hole is sealed with butyl rubber, and then a small piece of a titanium metal plate is used for the injection hole using an epoxy resin. Was pasted. Moreover, the secondary seal | sticker was performed to the peripheral part with the same epoxy resin. When the cell thus obtained was irradiated with pseudo-sunlight (1 kW / m ² ) and the current-voltage characteristics were measured, good photoelectric conversion characteristics (conversion efficiency 3.2%) were obtained. Moreover, the produced cell was bendable to 90 degree | times, and after bending, it returned to the original state and the change was not seen even if it measured the photoelectric conversion characteristic.

It is sectional drawing of a bus bar. It is an example of a bus bar pattern. It is explanatory drawing of a coverage.

Explanation of symbols

1 Transparent substrate 2 Bus bar
3 Busbar executives
4 Busbar branch
5 Busbar busbar
6 Active area (Sa)
7 Busbar area (Sb) of covering part

Claims (3)

  For a semiconductor layer modified with a sensitizer provided on a metal foil, an electrolyte layer containing a substance exhibiting at least reversible electrochemical redox characteristics, and a substance exhibiting the reversible electrochemical redox characteristics A flexible dye-sensitized solar cell comprising at least a counter electrode in which a bus bar made of a mixture containing at least a catalytic substance and metal particles is fixed to a transparent substrate by a screen printing method.   2. The flexible dye-sensitized solar cell according to claim 1, wherein a material selected from titanium, chromium, tungsten, platinum, various stainless steels and alloys thereof is used as the metal foil. The flexible dye-sensitized solar cell according to claim 1, wherein a material selected from carbon materials is used as the substance having a catalytic action.

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