JP2002289273A - Pigment sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment sensitized solar cell easily controlling electrolyte composition and simplify a working process during manufacturing. SOLUTION: This cell comprises a transparent substrate, a transparent conductive film formed on the substrate, and a conductive substrate mounted on a place opposite to the film and has a porous semiconductor layer that has absorbed pigment and electrolyte between the film and the substrate. The electrolyte is gel electrolyte containing an oxidation-reduction agent and a solvent that can dissolve the agent in a network structure cross-linking a compound A having at least one kind of isocyanate group with a compound B having at least one kind of carboxyl group and/or hydroxyl group. At least one kind of the compounds A, B is a compound with a high polymer structure of molecular weight of 500-100,000. A part or the whole of the high polymer structure is of one or more kinds selected from a group consisting of polyether, polyester, polycaprolactone, polysiloxane, polyvynil pyrrolidone, polycarbonate and polyphosphazene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye-sensitized solar cell, and more particularly, to a network formed by crosslinking a compound having a specific structure, containing a redox compound and a solvent capable of dissolving the redox compound. The present invention relates to a dye-sensitized solar cell using the gel electrolyte.

[0002]

2. Description of the Related Art Dye-sensitized solar cells have received widespread attention because of their high conversion efficiency among organic solar cells. As a semiconductor layer made of a photoelectric conversion material used in the dye-sensitized solar cell, a semiconductor layer having a spectral sensitizing dye having absorption in a visible light region adsorbed on a semiconductor surface is used.

For example, Japanese Patent Publication No. 2664194 describes a dye-sensitized solar cell using a metal oxide semiconductor layer in which a spectral sensitizing dye composed of a transition metal complex is adsorbed on the surface of a semiconductor layer. I have.

[0004] Japanese Patent Publication No. 8-15097 discloses that
On the surface of the titanium oxide semiconductor layer doped with metal ions,
A dye-sensitized solar cell having a spectral sensitizing dye layer such as a transition metal complex is described. Further, Japanese Patent Application Laid-Open No. 7-249
No. 790 describes a dye-sensitized solar cell using a semiconductor layer for a photoelectric conversion material obtained by heating and refluxing an ethanol solution of a spectral sensitizer on the surface of a semiconductor layer.

A process for producing a dye-sensitized solar cell using a general electrolytic solution will be described with reference to FIG.

FIG. 1 is a schematic sectional view showing the structure of a conventional dye-sensitized solar cell.

First, a transparent conductor film 12 is formed on the surface of a transparent support 11, a porous semiconductor layer 13 such as titanium oxide is formed thereon, and a dye is adsorbed on the porous semiconductor layer 13. Next, a catalyst such as a platinum film 16 is coated on the counter electrode 15, and the transparent support 11 and the counter electrode 15 are overlapped so that the porous semiconductor layer 13 and the platinum film 16 face each other. Further, the side surfaces of the transparent support 11 and the counter electrode 15 are sealed with an epoxy resin 17 or the like, and an electrolytic solution containing a redox substance is injected between them to form the electrolytic solution layer 14, whereby the dye-sensitized solar cell is manufactured. It is made.

In order to prevent liquid leakage from the electrolyte layer 14, Japanese Patent Application Laid-Open Nos. Hei 8-236165 and Hei 9-273
No. 52 describes a dye-sensitized solar cell in which an electrolyte layer is solidified. The following method is known as a method for solidifying the electrolyte layer.

First, the following general formula:

Embedded image (Wherein R ¹ and R ² are a hydrogen atom or a methyl group;
R ³ is a hydrogen atom or a lower alkyl group having 1 or more carbon atoms. n is an integer of 1 or more, m is an integer of 0 or more, and m / n ranges from 0 to 5. In the monomer solution obtained by dissolving the monomer represented by the formula (1) in ethylene glycol, an iodine compound (such as lithium iodide) which is a redox substance is dissolved and impregnated into the porous semiconductor layer. Polymerization is performed by heat to produce a polymer compound. After that, an electrolyte layer solidified by doping by sublimating iodine, which is another redox substance, is formed.

Japanese Patent Application Laid-Open No. 7-320772 (Sanyo Electric) describes an example of a gel electrolyte using urethane as a lithium ion conductor. In this case, three or more types of monomers are used, and the gel electrolyte is produced by impregnating a polymer compound with an electrolyte solution.

[0011]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 9-273 is disclosed.
In No. 52, a photoelectric conversion element using a crosslinked product of a polyether-based monomer is mentioned. In this case, since the monomer crosslinking is performed by radical polymerization, iodine used in a dye-sensitized solar cell is a monomer before crosslinking. , There is a problem that polymerization is inhibited. In addition, since iodine is injected after the polymerization, it is difficult to quantify the iodine concentration in the gel electrolyte.

Further, Japanese Patent Application Laid-Open No. 7-320772 discloses that
It relates to a solid electrolyte secondary battery, and does not describe a method for producing an electrolyte inside an electrode. In addition, since the porous semiconductor layer of the dye-sensitized solar cell is formed of nano-order particles, the permeation of the gel electrolyte into the inside of the pores is only required for lithium secondary batteries using micro-order electrode materials. More difficult than if you were. Therefore, it is difficult to apply the technology disclosed in Japanese Patent Application Laid-Open No. 7-320772 to a dye-sensitized solar cell.

The present invention has been made in view of the above-mentioned problems of the prior art, and uses a monomer that undergoes polymerization and crosslinking reaction even if iodine or the like is present in the monomer before crosslinking, thereby providing a gel. An object of the present invention is to provide a dye-sensitized solar cell having a polymer electrolyte, in which the composition of the electrolyte can be controlled and the working steps during production are simplified.

[0014]

A dye-sensitized solar cell according to the present invention comprises a transparent substrate, a transparent conductive film formed on the surface of the transparent substrate, and a position opposed to the transparent conductive film. Having a conductive substrate, between the transparent conductive film and the conductive substrate, a porous semiconductor layer having a dye adsorbed, a dye-sensitized solar cell having an electrolyte, the electrolyte, A network structure formed by crosslinking a compound A having at least one type of isocyanate group and a compound B having at least one type of carboxyl group and / or hydroxyl group contains a redox compound and a solvent capable of dissolving the redox compound. Gel electrolyte, wherein at least one of the compounds A and B has a molecular weight of 500 to 100,000.
A compound having a polymer structure of 0, wherein a part or the whole of the polymer structure is polyether, polyester, polycaprolactone, polysiloxane, polyvinylpyrrolidone,
One or more types selected from the group consisting of polycarbonate and polyphosphazene (claim 1).

As the solvent, one or more kinds selected from the group consisting of carbonates, ethers, lactones, nitriles and alcohols can be used (claim 2).

As the redox substance, one composed of iodine and an iodine compound can be used (claim 3).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The dye-sensitized solar cell of the present invention comprises:
In a dye-sensitized solar cell having a porous semiconductor layer and an electrolyte layer in which a dye is adsorbed between a transparent conductive film and a conductive substrate formed on the surface of a transparent substrate, a redox substance in the electrolyte layer includes: It is characterized by being held by a network structure formed by crosslinking a compound having an isocyanate group and a compound having an amino group.

Compound A having the above isocyanate group
May be a compound having one or more isocyanate groups in one molecule. Specifically, (A1) aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and xylylene diisocyanate; (A2) aliphatic isocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; (A3) isophorone diisocyanate; Alicyclic isocyanates such as cyclohexyl diisocyanate include (A1) to (A1).
Multimers such as dimers and trimers of 3) and denatured products may be used.

Further, (A4) an adduct of a low molecular weight alcohol and an aromatic isocyanate, an aliphatic isocyanate, or an alicyclic isocyanate, (A5) a compound having a high molecular structure and an isocyanate of the above specific example were previously subjected to an addition reaction. Examples of the compound include prepolymers having one or more isocyanate groups and having a molecular weight of 500 to 100,000.

Here, the compound having a polymer structure is
A compound having a functional group reactive with an isocyanate group, preferably one or more active hydrogen groups.

The polymer structure is partially or wholly composed of polyether, polyester, polycaprolactone, polyhexamethylene carbonate, polysiloxane, polyolefin, polybutadiene, polyisoprene, polystyrene, polyvinylpyridine, polyvinylmethylether,
Polyvinyl isobutyl ether, polyacrylic acid, polymethacrylic acid, alkyl polyacrylate, alkyl polymethacrylate, polyacrylamide,
Polyacrylonitrile, polyvinylidene anide, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl pyrrolidone, polyvinyl carbazole, polyethylene terephthalate, nylon, polyamide, polyimide , Polycarbonate, polybenzimidazole, polyamine, polyimine, polysulfide, polyphosphazene, or a natural polymer.

Among them, polyether, polyester, polycaprolactone, polysiloxane, polyolefin, polybutadiene, polyisoprene, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone, polycarbonate, polyphosphor Those having Zen are desirable.

Examples of the active hydrogen group include -SH
Group, -NH group, -NH₂Group, -CONH₂Group, -NHC
ONH- group, -NHCOO- group, Na⁺[CH (COO
C₂H ₅)] Group, -CH₂NO₂Group, -OOH group, -S
iOH group, -B (OH)₂Group, -PH₃Groups
And -NH₂Groups are preferred.

As the compound A having an isocyanate group, two or more of the above compounds may be used in combination.

On the other hand, the compound B is a compound having one or more carboxyl groups and / or hydroxyl groups in one molecule.

Specific examples of the compound having a carboxyl group include carboxylic acids such as hexanoic acid, adipic acid, phthalic acid and azelaic acid, and specific examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, glycerin and pentaerythritol. Sorbitol, sucrose and the like.

The compound B may have one or more carboxyl groups and / or hydroxyl groups in one molecule.
It may be a compound having a high molecular structure having a molecular weight of 500 to 100,000.

The polymer structure is partially or wholly composed of polyether, polyester, polycaprolactone, polyhexamethylene carbonate, polysiloxane, polyisoprene, polystyrene, polyvinylpyridine, polyvinylmethylether, polyvinylisobutylether, polyacrylamide, Polyacrylonitrile, polyvinylidene anide, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polyvinylcarbazole, polyethylene terephthalate, nylon,
It is preferable to be composed of polyamide, polyimide, polycarbonate, polybenzimidazole, polyamine, polyimine, polysulfide, or polyphosphazene.

Among them, those having polyether, polyester, polycaprolactone, polysiloxane, polyvinylpyrrolidone, polycarbonate, or polyphosphazene are particularly desirable.

As compound B, two of these compounds
More than one type can be used in combination.

The mixing ratio between the compound A and the compound B differs depending on the combination of the compound A and the compound B, and can be appropriately determined depending on the cross-linking property of the polymer and the performance required for the dye-sensitized solar cell.

In the present invention, a gel electrolyte is composed of a network structure formed by crosslinking the compound A and the compound B, and an electrolytic solution injected into the network structure.

The electrolytic solution is composed of a redox body and a solvent. These may be those which can be generally used in batteries and solar cells, and are not particularly limited. Preferred examples include the following. .

As the redox substance, LiI, NaI, K
A combination of a metal iodide such as I, CaI ₂ and iodine, and a combination of a metal bromide such as LiBr, NaBr and CaBr ₂ and a bromine are preferable, and among these, a combination of a metal iodide and iodine is particularly preferable.

The concentration of the redox substance is usually 0.1 to 1.5.
It is in the range of mol / l, and particularly preferably in the range of 0.5 to 1.5 mol / l.

The solvent is preferably an aprotic solvent, and examples thereof include cyclic esters, cyclic carbonates, cyclic ethers, chain carboxylic esters, chain carbonates, and sulfolane. Is mentioned. One of these solvents may be used, or two or more of them may be used.

In a solar cell, the conversion efficiency becomes poor unless the gel electrolyte is sufficiently injected into the porous semiconductor. For this reason, it is preferable to impregnate the porous semiconductor with the mixed solution of the electrolytic solution, the compound A, and the compound B, and then to crosslink the porous semiconductor. At this time, the order of mixing the electrolytic solution, the mixed solution of the compound A, and the compound B can be appropriately selected depending on the reactivity of each.

As a crosslinking method, a thermal crosslinking method is mainly applied. Crosslinking conditions vary depending on the type and combination of compound A and compound B, or the use or non-use of a catalyst. Therefore, conditions suitable for each system may be appropriately selected, but the crosslinking temperature is usually 0 ° C to 90 ° C. Is preferable.

At the time of crosslinking, a catalyst may be used. Usable catalysts include organometallic catalysts and amine catalysts, such as those commonly used in producing polyurethane foams. Specifically, examples of organometallic catalysts include stannas octoate, stannas oleate, dibutyltin dilaurate, and dibutyltin diacetate. Examples of amine catalysts include triethylamine, tributylamine, N-methylmorpholine, and N-ethyl. Examples include morpholine, pyridine, and triethylenediamine.

The amount of the catalyst to be added is usually 0.001 to 5 with respect to the total weight of the compound A, the compound B and the electrolyte solution.
wt%.

Examples of the porous semiconductor constituting the porous semiconductor layer include known semiconductors such as titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, and cadmium sulfide. These porous semiconductors can be used as a mixture of two or more kinds.
Among them, titanium oxide is particularly preferred from the viewpoint of conversion efficiency, stability and safety. Examples of such titanium oxides include various titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, and orthotitanic acid, and titanium oxide-containing composites. One type or two or more types can be appropriately used.

As the porous semiconductor, various forms such as a particle form and a film form can be used, but a film-like porous semiconductor formed on a substrate is preferable.

Preferred examples of the substrate for forming the film-shaped porous semiconductor include a glass substrate and a plastic substrate, and among them, a highly transparent substrate (transparent substrate) is particularly preferred.

As a method for forming a film-like porous semiconductor on a substrate, various known methods can be used.

Specifically, (1) a method of applying a suspension containing semiconductor particles on a substrate, followed by drying and baking, (2)
CVD or MOC using desired source gas on substrate
A method of forming a semiconductor film by a VD method or the like; (3) a method of forming a semiconductor film by a PVD method using a raw material solid, an evaporation method, a sputtering method, a sol-gel method, or the like; A method of forming by an oxidation-reduction reaction may be mentioned.

The thickness of the porous semiconductor film is not particularly limited, but may be selected from the viewpoints of permeability, conversion efficiency, and the like.
About 0.5 to 20 μm is desirable. Further, in order to improve the conversion efficiency, it is necessary to make the film-like porous semiconductor adsorb more dyes described later. For this,
The film-shaped porous semiconductor desirably has a large specific surface area, specifically, preferably about 10 to 200 m ² / g.

As the above-mentioned semiconductor particles, commercially available semiconductors have an appropriate average particle diameter, for example, 1 nm to 50 nm.
Single or compound semiconductor particles having an average particle size of about 0 nm can be used. Examples of solvents used for suspending the semiconductor particles include glyme solvents such as ethylene glycol monomethyl ether, alcohols such as isopropyl alcohol, mixed solvents such as isopropyl alcohol / toluene, and water. Can be

The drying and baking of the porous semiconductor described above include:
Depending on the type of substrate and semiconductor particles used, temperature, time,
The atmosphere is adjusted as appropriate. In a general example, the heat treatment is performed for about 10 seconds to 12 hours in a temperature range of about 50 to 800 ° C. in the atmosphere or an inert gas atmosphere. The drying and baking may be performed only once at a single temperature, or may be performed two or more times at different temperatures.

The transparent conductive film that can be used as an electrode is not particularly limited.
(Indium-tin oxide), a transparent conductive film such as SnO ₂ are preferable. These electrodes can be formed by a method such as vacuum evaporation, and the thickness and the like can be appropriately selected.

As a method of adsorbing a dye functioning as a photosensitizer (hereinafter simply referred to as “dye”) on the porous semiconductor layer, for example, the porous semiconductor layer formed on a substrate is adsorbed with the dye. A method of dipping in a dissolved solution may be mentioned.

The dye which can be used here has an absorption in various visible light regions and infrared light regions, and a carboxyl group, an alkoxy group or an alkoxy group is contained in the dye molecule in order to strongly adsorb the semiconductor layer. Those having an interlock group such as a group, a hydroxyl group, a hydroxyalkyl group, a sulfonic acid group, an ester group, a mercapto group and a phosphonyl group are preferred.

The interlock group provides an electrical bond that facilitates electron transfer between the dye in the excited state and the semiconductor conductor. Examples of dyes containing these interlock groups include, for example, ruthenium bipyridine dyes, azo dyes, quinone dyes, quinone imine dyes,
Quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, phthalocyanine dyes, berylen dyes, indigo dyes, naphthalocyanine dyes, and the like. .

Examples of solvents used for dissolving the dye include alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, nitrogen compounds such as acetonitrile, and halogenated aliphatics such as chloroform. Hydrocarbons, aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene,
Esters such as ethyl acetate are exemplified.

The concentration of the dye in the solution can be appropriately adjusted depending on the type of the dye and the solvent to be used. To improve the adsorption function, it is preferable that the concentration is somewhat high. For example, a concentration of 5 × 10 ⁻⁵ mol / liter or more is preferable.

When the semiconductor is immersed in the solution in which the dye is dissolved, the temperature and the pressure of the solution and the atmosphere are not particularly limited. For example, the temperature and the pressure are about room temperature and the atmospheric pressure. It is preferable to appropriately adjust according to the type of dye to be used, the type of solvent, the concentration of the solution, and the like. In addition, in order to perform adsorption effectively, immersion may be performed under heating.

[0056]

Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 A dye-sensitized solar cell using a solid polymer electrolyte was prepared by the following method, and its conversion efficiency was evaluated.

Regarding a method for producing a dye-sensitized solar cell,
This will be described with reference to FIG. FIGS. 2A to 2C are schematic cross-sectional views of a dye-sensitized solar cell in which a manufacturing procedure is followed. In FIG. 2, reference numeral 1 denotes a transparent substrate, reference numeral 2 denotes a transparent conductive film,
Reference numeral 3 indicates a titanium oxide film, reference numeral 4 indicates a separator, and reference numeral 5
Denotes a platinum film, 6 denotes a conductive substrate, and 7 denotes a polymer solid electrolyte layer (gel electrolyte layer).

A transparent conductive film 2 made of SnO ₂ was formed on a transparent substrate 1 made of glass by vacuum evaporation, and a titanium oxide film 3 was formed on the transparent conductive film 2 by the following method.

As the titanium oxide suspension for forming the titanium oxide film 3, a commercially available titanium oxide suspension (Sola) is used.
manufactured by Ronix, Inc., trade name: Ti-Nanoxide D)
It was used. This titanium oxide suspension was applied to the transparent conductive film 2 side with a thickness of about 10 μm and an area of about 10 mm × 10 mm using a doctor blade method, and was preliminarily dried at 80 ° C. for 30 minutes. Bake in air for minutes. As a result, a titanium oxide film 3 having a thickness of about 7 μm was obtained.

[0061] Next ruthenium dye (Kojima Chemical Co., Ltd., trade name: Ruthenium complex) was dissolved in absolute ethanol at a concentration of 4 × 10 ^-4 mol / l, was prepared adsorbing dye solution. A transparent substrate 1 having the dye solution for adsorption, the titanium oxide film 3 and the transparent conductive film 2 obtained above.
Was placed in a container, boiled for 1 minute, and allowed to stand for 10 minutes, so that the dye was adsorbed on the titanium oxide film 3.
Then, it is washed several times with absolute ethanol, and
Dry for 0 minutes.

Next, an electrolytic solution to be held in the gel was prepared. That is, an electrolyte was prepared by dissolving lithium iodide at a concentration of 0.5 mol / l and iodine at a concentration of 0.05 mol / l using propylene carbonate (hereinafter referred to as PC) as a solvent.

As a compound A, 11.3 g of a compound synthesized by the following synthesis method 1, as a compound B, 1 g of a polyester polyol (trade name: Phantol PL-180, manufactured by Toho Rika Co., Ltd.), 110.7 g of an electrolytic solution, and triethylamine as a catalyst 0.002 g was used.

(Synthesis method 1) In a reaction vessel, 92 g of glycerin as a starting material and potassium hydroxide 3 as a catalyst
0 g, and ethylene oxide 5,950 g
And 3,970 g of propylene oxide, and 130
After a reaction at 10 ° C. for 10 hours, a neutralization dehydration treatment was performed to obtain a trifunctional ethylene oxide-propylene oxide copolymer having a molecular weight of 10,000. Compound 100 obtained
Then, 5.3 g of tolylene diisocyanate and 0.05 g of dibutyltin dilaurate as a catalyst were added thereto, and reacted at 80 ° C. for 3 hours to obtain a compound having a molecular weight of 10,520.

This monomer solution is applied to the titanium oxide film 3 described above.
The procedure for impregnation is shown below. (1) A container such as a petri dish is set in a vacuum container, the titanium oxide film 3 on the transparent substrate 1 provided with the transparent conductive film 2 is put therein, and the vacuum is evacuated by a rotary pump for about 10 minutes. (2) The monomer solution is poured into a petri dish while keeping the vacuum container in a vacuum state, and immersed for about 10 minutes, so that the monomer solution is sufficiently permeated into the titanium oxide 3 film. (3) FIG. 1 (c)
As shown in (1), a conductive substrate 6 having a polyimide separator 4 and a platinum film 5 is installed and fixed with a jig. Thereafter, by heating at about 90 ° C. for 60 minutes, thermal crosslinking is performed to form the gel electrolyte layer 7.

It was confirmed that the dye-sensitized solar cell containing the gel electrolyte layer 7 formed by the above-described method had the same conversion efficiency as the solar cell using the liquid electrolyte. Specifically, the short-circuit current is 14.7 [mA /
cm ² ], an open-circuit voltage of 0.70 [V], a fill factor of 0.68, and a conversion efficiency of 7.0 [%] (measurement conditions: A
A dye-sensitized solar cell having a performance of M-1.5 (100 mW / cm ² ) was obtained.

In the following Examples 2 to 11, the gel electrolyte layer 7 was formed by changing the compound A and the compound B, and the other steps and constituent materials were the same as those in the example 1 in the dye-sensitized solar cell. Was prepared. The conversion efficiency of each of these dye-sensitized solar cells was measured. Table 1 shows the results. In addition, about the compound synthesize | combined by the present inventors, the synthesis method is also shown.

Example 2 0.35 g of tolylene diisocyanate as compound A, 5 g of compound B synthesized by the following synthesis method 2 and 5 g of compound synthesized by the following synthesis method 3, 93.15 g of electrolytic solution, and 0.01 g of eggplant octoate was used.

(Synthesis Method 2) Glycerin 9 in a reaction vessel
Starting from 2 g of propylene oxide 1910
g was added to obtain a trifunctional propylene oxide polymer having a molecular weight of 2,000.

(Synthesis method 3) Starting from 62 g of ethylene glycol in a reaction vessel, 6,960 g of ethylene oxide and 2,990 g of propylene oxide were subjected to an addition reaction to obtain a bifunctional ethylene oxide-propylene oxide having a molecular weight of 10,000. A copolymer was obtained.

Example 3 8 g of tolylene diisocyanate as compound A, 9 g of compound B synthesized by the following synthesis method 4 and 1 g of compound synthesized by the following synthesis method 5, 72 g of electrolytic solution, and 0.1 g of triethylenediamine as a catalyst. 01 g was used.

(Synthesis Method 4) Starting from 62 parts by weight of ethylene glycol in a reaction vessel, an addition reaction of 138 parts by weight of ethylene oxide was carried out to obtain polyethylene glycol having a molecular weight of 200.

(Synthesis Method 5) In a reaction vessel, 60 g of vinylpyrrolidone and 138 g of water were mixed and mixed at 25 ° C. for 1 wt.
% Copper sulfate 0.003g, 28wt% ammonia water 0.3
g and 1.4 g of a 30 wt% hydrogen peroxide solution were added to carry out polymerization, which was dehydrated to obtain polyvinylpyrrolidone having a K value of 30.

Example 4 As compound A, 0.03 g of isophorone diisocyanate, as compound B, 10 g of a compound synthesized by the following synthesis method 6, 90.3 g of electrolyte solution,
0.01 g of dibutyltin dilaurate was used as a catalyst.

(Synthesis Method 6) Polydichlorophosphazene obtained by ring-opening polymerization of 250 parts by weight of hexachlorocyclotriphosphazene and sodium salt of 860 parts by weight of polyethylene glycol having a molecular weight of 230 were subjected to condensation polymerization to give a molecular weight of 95, 000 polyphosphazene polyol was obtained.

Example 5 2 g of tolylene diisocyanate as compound A and silicone as compound B (trade name: modified silicone oil FM-44, manufactured by Chisso Corporation)
11) 10 g, 68 g of electrolyte solution, and 0.01 g of triethylenediamine were used as a catalyst.

Example 6 As a compound A, 6 g of a compound synthesized by the following synthesis method 7, and as a compound B, 5 g of a polyether-modified polycarbonate diol (Placcel CD-221, manufactured by Daicel Chemical Industries, Ltd.)
99 g of electrolyte solution, 0.1 g of triethylenediamine as a catalyst.
005 g were used.

(Synthesis Method 7) Polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, trade name:
18 parts by weight of tolylene diisocyanate and 0.05 parts by weight of dibutyltin dilaurate as a catalyst were added to 100 parts by weight of PTMG2000 and reacted at 80 ° C. to obtain a compound having a molecular weight of 2,350.

Example 7 0.6 g of isophorone diisocyanate as compound A, 10 g of polycaprolactone (trade name: Placcel L230AL, manufactured by Daicel Chemical Industries, Ltd.), 95.4 g of electrolyte solution, and Stanasole as catalyst as compound B 0.01 g of Eat was used.

Example 8 36.8 g of compound A synthesized by the following synthesis method 8 as compound A, 0.5 g of compound B synthesized by the above synthesis method 2 as compound B, and electrolyte 3
36 g, triethylenediamine 0.005 as a catalyst
g was used.

(Synthesis Method 8) Starting from 62 parts by weight of ethylene glycol in a reaction vessel, 78,000 parts by weight of ethylene oxide and 19,60 parts of propylene oxide were used.
An addition reaction of 0 parts by weight was performed to obtain a bifunctional ethylene oxide-propylene oxide copolymer having a molecular weight of 97,700. To 100 parts by weight of the obtained compound were added 0.4 parts by weight of hexamethylene diisocyanate, 0.1 parts by weight of dibutyltin dilaurate as a catalyst, and 100 parts by weight of methyl ethyl ketone as a diluting solvent. Removal of methyl ethyl ketone to give a molecular weight of 9
8,000 compounds were obtained.

Example 9 13.6 g of the compound A obtained by the following synthesis method 9, 0.3 g of polyethylene glycol having a molecular weight of 200 as the compound B, 0.7 g of the compound obtained by the following synthesis method 10, Liquid 13
1 g and 0.1 g of triethylenediamine as a catalyst were used.

(Synthesis Method 9) In a reaction vessel were charged 62 g of ethylene glycol as a starting material and 30 g of potassium hydroxide as a catalyst.
After 340 g and 1,570 g of propylene oxide were charged and reacted at 130 ° C. for 10 hours, a neutralization dehydration treatment was performed to obtain a bifunctional ethylene oxide-propylene oxide copolymer having a molecular weight of 7,960. Hexamethylene diisocyanate 4.2 was added to 100 g of the obtained compound.
g, dibutyltin dilaurate 0.1 g as a catalyst,
100 g of methyl ethyl ketone as a diluting solvent was added and reacted at 80 ° C. After the reaction, methyl ethyl ketone was removed to obtain a compound having a molecular weight of 8,300.

(Synthesis Method 10) In a reaction vessel, 92 g of glycerin as a starting material and 24 g of potassium hydroxide as a catalyst were charged.
g and 1,590 g of propylene oxide.
After reacting at 30 ° C. for 8 hours, neutralization dehydration treatment was performed to obtain a trifunctional ethylene oxide-propylene oxide copolymer having a molecular weight of 8,000. Compound 100 obtained
g and 4.1 g of chloroacetic acid methyl ester were reacted at 60 ° C. in the presence of an alkali catalyst to form an alcoholate, followed by sulfuric acid treatment to obtain 90 g of a carboxyl group-modified polyether having a molecular weight of 8,140.

Example 10 As a compound A, 1.6 g of the compound obtained by the following synthesis method 11, as a compound B, 10 g of a compound obtained by the following synthesis method 12, 104 g of an electrolyte solution, and stanna octoate 0 as a catalyst .01
g was used.

(Synthesis Method 11) In a reaction vessel, 53.4 g of a polyester polyol (manufactured by Toho Rika Co., Ltd., trade name: Phantol PL-2010) and 34.8 g of tolylene diisocyanate were mixed, and dibutyltin as a catalyst was mixed. 0.05 g of dilaurate was added and reacted at 80 ° C. to obtain a compound.

(Synthesis method 12) 106 g of diethylene glycol as a starting material and 24 g of potassium hydroxide as a catalyst were charged into a reaction vessel, and 2,940 g of ethylene oxide and 1,980 g of propylene oxide were further charged, and the mixture was heated at 130 ° C. for 8 hours. After the reaction, a neutralization dehydration treatment was performed to obtain a bifunctional ethylene oxide-propylene oxide copolymer having a molecular weight of 4,980. 100 g of the obtained compound and 4.5 g of chloroacetic acid methyl ester
Was reacted at 60 ° C. in the presence of an alkali catalyst to form an alcoholate, followed by sulfuric acid treatment to obtain 90 g of a carboxyl group-modified polyether having a molecular weight of 5,000.

[Example 11] As compound A, 2 g of the compound obtained by the above synthesis method 11, as compound B, 10 g of carboxyl group-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-162C), electrolysis Liquid 10
8 g, and 0.01 g of stanna octoate as a catalyst were used.

[0089]

[Table 1]

As shown in Table 1, there was a difference in the conversion efficiency of the dye-sensitized solar cells by changing the compounds A and B. In addition, the longer the molecular chain as a whole, the higher the conversion efficiency was obtained. This is presumably because the longer the molecular chain, the larger the network of the produced polymer compound, the stronger the holding power of the redox electrolyte, and the higher the conversion efficiency.

[0091]

According to the present invention, since the redox electrolyte is stably and abundantly held in the three-dimensional network of the polymer compound, the ionic conductivity is at the same level as that of the polymer-free redox electrolyte. A dye-sensitized solar cell having a polymer electrolyte having a high efficiency can be manufactured by simplifying the operation steps as compared with the related art, and the control of the electrolyte composition becomes easy.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of a main part of a conventional dye-sensitized solar cell.

FIG. 2 is a schematic cross-sectional view illustrating a procedure for manufacturing a dye-sensitized solar cell using a polymer electrolyte according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 transparent substrate 2 transparent conductive film 3 titanium oxide film 4 separator 5 platinum film 6 conductive substrate 7 gel electrolyte layer 11 transparent support 12 transparent conductive film 13 porous semiconductor layer 14 electrolyte layer 15 counter electrode 16 platinum film 17 epoxy resin

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Han Regen 22-22, Nagaike-cho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Corporation (72) Inventor Yoshiaki Yamanaka 22-22, Nagaike-cho, Abeno-ku, Osaka-shi, Osaka (72) Inventor Eriko Ishiko 187-1 Kita-zai, Kakogawa-cho, Kakogawa-shi, Hyogo Prefecture 3rd Meinobu Building 301 (72) Inventor Michiyuki Kono 14-1 Korihondoricho, Neyagawa-shi, Osaka F-term (reference) 5F051 AA14 FA03 FA06 GA03 5H032 AA06 AS16 CC06 CC11 CC17 EE02 EE03 EE04 EE16 HH00

Claims (3)

[Claims] A transparent conductive film formed on a surface of the transparent substrate; and a conductive substrate provided at a position opposed to the transparent conductive film. A dye-sensitized solar cell having a porous semiconductor layer in which a dye is adsorbed, and an electrolyte, between the conductive substrate and the conductive substrate, wherein the electrolyte has at least one compound A having at least one isocyanate group; and And a gel electrolyte containing a redox body and a solvent capable of dissolving the redox body in a network structure formed by crosslinking a compound B having a carboxyl group and / or a hydroxyl group. At least one kind is a compound having a polymer structure having a molecular weight of 500 to 100,000, and a part or the whole of the polymer structure is polyether, polyester, polycaprolactone, Polysiloxane, polyvinylpyrrolidone, polycarbonate, and poly phosphatonin dye-sensitized solar cell characterized by being selected from the group consisting of Zen is one kind or two or more kinds. 2. The solvent according to claim 1, wherein the solvent is one or more selected from the group consisting of carbonates, ethers, lactones, nitriles, and alcohols. Dye-sensitized solar cells. 3. The dye-sensitized solar cell according to claim 1, wherein the redox body is composed of iodine and an iodine compound.