JP2012109189A - Polymer electrolyte for dye sensitized solar cell and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and efficiently provide a polymer electrolyte for a dye sensitized solar cell, having favorable photoelectric conversion efficiency, and excellent in durability and shape stability.SOLUTION: A polymer electrolyte composition for a dye sensitized solar cell includes: (i) a polymer represented by formula (1) [in the formula, A represents a residue of an active hydrogen-containing compound, R represents an alkyl group having 1-12 carbon atoms or the like, and m, n and p represent an integer of 1 to 1,200, an integer of 0 to 25, and an integer of 1 to 12, respectively.]; and (ii) an electrolyte containing a redox pair.

Description

  The present invention relates to a polymer electrolyte used in a dye-sensitized solar cell and its use.

  Conventionally, single crystal silicon, polycrystalline silicon solar cells, and amorphous silicon solar cells are commercially available as solar cells that generate electricity using sunlight, which is clean energy, but each has a problem of high manufacturing costs.

  On the other hand, other than these silicon solar cells, there are solar cells using an organic compound as the electrolyte of the photoelectric conversion layer. Among them, a dye-sensitized solar cell obtains a photovoltaic power using an organic dye, and a typical type is called a Gretzell type.

This Gretzell solar cell has a structure in which an electrolyte is sandwiched between a titanium dioxide layer or a zinc oxide layer in which a small amount of a dye such as a ruthenium complex is adsorbed between two transparent electrodes.
This Gretzel type solar cell has advantages such as being lightweight and capable of being colored, and having a simple structure, widely developed materials, and relatively inexpensive. Compared to this, it is expected that the production cost can be significantly reduced.

  For these reasons, a wet type electrolyte using an electrolytic solution has been widely studied as an organic compound electrolyte used in a dye-sensitized solar cell (for example, “Non-Patent Document 1”). The electrolytic solution used in this dye-sensitized solar cell is known to have a high photoelectric conversion rate when a nitrile compound, a cyclic carbonate, a cyclic ester, or the like, which is an aprotic solvent, is used. in use.

  However, this type of wet solar cell is relatively susceptible to electrolyte leakage and volatilization, which significantly reduces the photoelectric conversion efficiency, and if it is damaged, the flammable electrolyte leaks and is dangerous. In addition, there is a drawback that there is a risk of damage due to an increase in the internal pressure of the battery cell due to evaporation of the electrolyte.

  Therefore, in order to prevent this liquid leakage, a polymer electrolyte obtained by impregnating a polymer with an electrolytic solution has been studied. And there is an example of using polyacrylonitrile, which is a polymer having a nitrile group that seems to be effective for improving photoelectric conversion efficiency, as a solid electrolyte by quasi-solidification, but the photoelectric conversion efficiency is low and sufficient photoelectric conversion efficiency is expressed. A thing is not obtained (for example, "patent document 1").

  When such a polymer is used as an electrolyte as it is, an electrolyte layer is usually formed between the electrodes by a method such as applying a high viscosity polymer solution directly to the electrodes. It is also possible to inject it. However, in the case of direct injection into the battery cell, there arises a problem that, if the oxide semiconductor fine particles cannot be properly impregnated into the pores of the electrode, the conductive characteristics are not exhibited.

JP 2002-289270 A

Nature, 353 (24), 737-740 (1991)

  In view of the circumstances as described above, the object of the present invention is to provide an industrially useful polymer electrolyte for dye-sensitized solar cells that has excellent workability, good photoelectric conversion efficiency, and excellent durability and shape stability. It is to provide efficiently.

  The present invention relates to a composition for a polymer electrolyte for a dye-sensitized solar cell comprising an electrolyte containing a polymer of the following formula (1) and a redox couple, and a dye sensitizer having a crosslinking ability in which a crosslinking agent is further present. Provided are a polymer electrolyte composition for a solar cell and a dye-sensitized solar cell using the same.

[式中、Ａは活性水素含有化合物残基、Ｒは炭素数１〜１２のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜８のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１２のアラルキル基の群より選ばれる少なくとも一つの基である。また、ｍは1〜1,200の整数、ｎは0〜25の整数、ｐは1〜12の整数をそれぞれ表わす。]
(ii)酸化還元対を含む電解液、
からなることを特徴とする、色素増感太陽電池用高分子電解質組成物である。 Item 1 of the present invention
(i) a glycidyl ether polymer represented by formula (1) (when n = 0) or a polyether polymer having an oxyethylene unit in the side chain (when n ≠ 0);

[Wherein, A is an active hydrogen-containing compound residue, R is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl having 6 to 14 carbon atoms. And at least one group selected from the group of aralkyl groups having 7 to 12 carbon atoms. M represents an integer of 1 to 1,200, n represents an integer of 0 to 25, and p represents an integer of 1 to 12, respectively. ]
(ii) an electrolyte containing a redox couple,
A polymer electrolyte composition for a dye-sensitized solar cell, comprising:

  Item 2 of the present invention further comprises (iii) at least one crosslinking agent selected from compounds having two or more isocyanate groups in the composition according to Item 1 of the present invention. Item 2. The polymer electrolyte composition for a dye-sensitized solar cell according to Item 1.

  Item 3 of the present invention is the polymer electrolyte composition for a dye-sensitized solar cell according to Item 1 or 2, wherein the active hydrogen-containing compound residue A is derived from a polyhydric alcohol. is there.

  Item 4 of the present invention is that the crosslinking agent is 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI). ), Hexamethylene diisocyanate (HMDI), isophorone diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylolpropane The polymer electrolyte composition for a dye-sensitized solar cell according to claim 2 or 3, wherein the polymer electrolyte composition is a TDI3 molar adduct or at least one selected from the group consisting of any mixture thereof.

  Item 5 of the present invention is a polymer for a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the redox pair is a pair of iodine and iodine compound or bromine and bromine compound. It is an electrolyte composition.

  Item 6 of the present invention is the polymer electrolyte composition for a dye-sensitized solar cell according to any one of claims 1 to 5, wherein the electrolytic solution is an aprotic organic solvent.

  Item 7 of the present invention is a dye-sensitized solar cell using the polymer electrolyte composition for a dye-sensitized solar cell according to any one of claims 1 to 6.

  By using the present invention, the obtained polymer electrolyte composition for a dye-sensitized solar cell is excellent in workability and maintains good photoelectric conversion efficiency. In particular, the crosslinked product when the composition contains a crosslinking agent is excellent in durability and shape stability while maintaining good photoelectric conversion efficiency.

  Hereinafter, the configuration of the present invention will be described in detail.

The polymer of the formula (1) can be easily obtained, for example, by polymerizing the active hydrogen compound and the glycidyl ether represented by the formula (2) by a known method in the presence of a suitable catalyst. Further, the compound of the formula (2) itself can be easily synthesized by a general ether synthesis method from epihalohydrin and alcohol. In the monomer represented by the formula (2) obtained by synthesis, n is 0 to 25 and preferably 0 to 5. When n is larger than 25, the effect on charge transfer is reduced, which is not preferable.
R is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Preferably, R is selected from an alkyl group having 1 to 6, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 7 carbon atoms. More preferably, R is an alkyl group having 1 to 3, an alkenyl group having 2 to 3 carbon atoms, and a cycloalkyl group having 3 carbon atoms.
Here, R may have an element other than carbon in the skeleton, such as a heterocyclic ring, in addition to the functional group consisting of only the hydrocarbon, for example, a tetrahydropyranyl group or a tetrahydrofuranyl group. Preferably, it is a tetrahydropyranyl group.

  As a polyether polymer having a skeleton represented by the formula (1), a glycidyl ether represented by the formula (2) is added to an active hydrogen-containing compound in the presence of a catalyst, and the number average molecular weight is 1,000 to 100,000. It was obtained by reacting so that m in the formula (1) is 1-1200. Among them, those having a number average molecular weight of 1,000 to 5,000, that is, m of formula (1) of 1 to 50 are preferable. If m exceeds 1,200, the solution viscosity becomes high and impregnation into the pores of the electrode becomes insufficient.

  Examples of active hydrogen-containing compounds include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin; butylamine, 2-ethylhexylamine , Ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, benzylamine, phenylenediamine and other amine compounds; bisphenol-A, hydroquinone, novolac and other phenolic active hydrogen compounds; mono Examples include compounds having different active hydrogen-containing groups in one molecule such as ethanolamine and diethanolamine. Alcohol are preferred, glycerol, trimethylolpropane, trivalent or tetravalent alcohol pentaerythritol are more preferred.

The polymerization reaction can be performed as follows. Coordination anion initiator such as catalyst system mainly composed of organic aluminum, catalyst system mainly composed of organic zinc, organotin-phosphate ester condensate catalyst system as a ring-opening polymerization catalyst, or potassium containing K ⁺ as a counter ion Using an anionic initiator such as alkoxide, diphenylmethyl potassium or potassium hydroxide, the active hydrogen-containing compound and the monomer of formula (2) are reacted in the presence or absence of a solvent at a reaction temperature of 10 to 120 ° C. with stirring. To obtain a polyether polymer of the formula (1). In this case, at least one active hydrogen-containing group (for example, hydroxyl group) of the active hydrogen-containing compound constituting the obtained polyether polymer may be involved in the polymerization.
Anionic initiators such as potassium alkoxide, diphenylmethyl potassium, potassium hydroxide and the like containing K ⁺ in the counter ion are preferable from the viewpoint of the degree of polymerization or the properties of the resulting copolymer, and t-butoxy potassium is particularly easy to handle. Particularly preferred.

  The polyether polymer having a nitrile group used in the present invention is preferably 2 to 60% by weight, more preferably 5 to 30% by weight, based on the entire electrolyte.

  The polyether polymer can be crosslinked by using the following crosslinking agent.

Examples of the crosslinking agent include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate ( HMDI), isophorone diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylolpropane TDI 3 mol adduct, etc. It can be mentioned, and it can select suitably from single or these mixtures.
In this case, as a crosslinking mechanism, the polyether polymer having a nitrile group in the side chain of the formula (1) has a hydroxyl group at its terminal, and thus is crosslinked by a reaction with an isocyanate group possessed by a crosslinking agent. be able to. It is preferable to mix and react so that the number of isocyanate groups in the cross-linking agent is 0.1 to 5.0, preferably 0.5 to 2.0 times the hydroxyl groups of the polyether polymer of formula (1).

  In order to proceed the crosslinking reaction more effectively, for example, dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTA), phenylmercury propionate, lead octenoate and other organometallic compounds, triethylenediamine, N, N An amine compound such as' -dimethylpiperazine, N-methylmorpholine, tetramethylguanidine, triethylamine or the like may be used as a crosslinking catalyst.

The redox pair used in the present invention may be any redox pair that causes redox electrochemically, but is preferably a combination of iodine and an iodine compound or a combination of bromine and a bromine compound. Among them, a combination of I ₂ and an iodine salt such as LiI, or a combination of Br ₂ and a bromine salt such as LiBr is preferable. Various ionic liquids can be used instead of LiI.
For example, 1-propyl-2,3-dimethylimidazolium iodide, 1-methyl-2-ethyl-imidazolium iodide, 1-methyl-2-propylimidazolium iodide, 1-methyl-3-propylimidazolium Examples include imidazolium salts such as iodide, quaternary ammonium salts such as tetrapropylammonium iodide, and pyridinium salts such as 1-butyl-4-methylpyridinium iodide. When these ionic liquids are used, it is possible to use them without using a solvent. The concentration of the redox couple and the ionic liquid is preferably 0.1% by weight to 30% by weight, more preferably 0.2% by weight to 20% by weight, based on the entire electrolyte.

  The electrolytic solution used in the present invention may be an aprotic solvent, provided that it dissolves the electrolyte and does not separate from the crosslinked polyether polymer. It is preferably at least one selected from nitriles, cyclic or chain carbonates and cyclic esters. As the nitriles, acetonitrile, propionitrile, butyronitrile, methoxypropionitrile are preferable, as the cyclic carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and the like are preferable, and as the cyclic ester, γ-butyrolactone, γ -Lactones such as valerolactone and σ-butyrolactone are preferred. These solvents may be used alone, or may be used as a mixture of two or more. The amount of the electrolytic solution is preferably 10% by weight to 98% by weight with respect to the whole electrolyte, and more preferably 50% by weight to 95% by weight.

  The polymer electrolyte for dye-sensitized solar cell of the present invention can be used by impregnating the inside of the solar cell as it is. Moreover, when this electrolyte contains a crosslinking agent, it can be used as a crosslinked body using an appropriate crosslinking means such as heating after impregnation. In this case, since the polyether polymer is synthesized separately in advance, since there is almost no polymerization initiator at the time of polyether polymerization and there is almost no unreacted polyether polymer, the photoelectric conversion efficiency is not adversely affected. The photoelectric conversion efficiency can be maintained, and a highly durable polymer electrolyte composition for dye-sensitized solar cells and a crosslinked product thereof can be efficiently provided.

  The configuration of the dye-sensitized solar cell of the present invention is not particularly limited, and can be carried out with a conventional known basic configuration of a dye-sensitized solar cell except for the polymer electrolyte composition. As an example of the structure, a porous semiconductor composed of fine metal oxide particles carrying a sensitizing dye on one of two transparent conductive substrates coated with a transparent conductive film on one side of a transparent glass or plastic film. The electrode is provided with a layer, and the other is a counter electrode in which a conductive material is introduced on the surface, and an electrolyte is disposed between the pair of electrodes.

Examples of the semiconductor layer include Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si. Metal oxides such as Cr are used, but TiO ₂ or ZnO is particularly preferable. The semiconductor layer can be formed by, for example, applying a slurry liquid containing semiconductor fine particles to the surface of a substrate having electrodes by a known method, and then heat-sintering at a temperature in the range of 400 to 600 ° C. Is possible.

  The dyes adsorbed and supported on the semiconductor fine particles are ruthenium bipyridine dyes, azo dyes, quinone dyes, quinone imine dyes, cyanine dyes, triphenylmethane dyes, porphyrin dyes, phthalocyanine dyes, indigo dyes, Examples include phthalocyanine dyes, and ruthenium bipyridine dyes are particularly preferable because they have a wide absorption band in the visible light region.

As a method for supporting the dye on the semiconductor layer, a method in which a substrate provided with an electrode having a semiconductor layer is immersed in a dye solution in which a sensitizing dye is dissolved in a solvent, or a dye solution is applied to the semiconductor layer may be used. It is also effective to increase the efficiency of immersion by heating or applying ultrasonic waves during immersion.
As the solvent at this time, alcohols, nitriles, nitromethane, halogenated hydrocarbons, ethers, dimethyl sulfoxide, amides, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters Any of those that can dissolve sensitizing dyes such as solvents such as carbonates, ketones, hydrocarbons, and water can be used.

The conductive layer forming the semiconductor layer is formed on one surface of a transparent substrate such as glass or a film, and the electrode thus created serves as a negative electrode.
Examples of preferable conductive agents for forming the negative electrode conductive layer include metals such as platinum, gold, silver, copper, aluminum, rhodium and indium, carbon, or indium-tin composite oxide, fluorine. And conductive metal oxides such as tin oxide doped with.

  The other counter electrode serves as the positive electrode of the solar cell. Although it can be formed in the same manner as the electrode on the side where the semiconductor layer is provided, as a material for the counter electrode of the dye-sensitized solar cell in the present invention, platinum having a catalytic action to give electrons to the electrolyte reductant, Graphite or the like is preferable, and acts efficiently as the positive electrode of the solar cell.

  In the present invention, a basic compound such as tert-butylpyridine, 2-picoline, or 2,6-lutidine may be added to the aforementioned electrolyte for the purpose of preventing reverse electron transfer from the semiconductor layer to the electrolyte. preferable. A preferable concentration range when these basic compounds are added is 0.05 to 2 mol / L with respect to the electrolytic solution.

  In the present invention, it is preferable that the electrolyte contains a guanidine salt for the purpose of further increasing the photocurrent and further increasing the initial photoelectric conversion efficiency. An example of a guanidine salt is guanidine thiocyanate. A preferable concentration range when adding the guanidine salt is 0.02 to 0.5 mol / L with respect to the electrolytic solution.

EXAMPLES Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

  In measuring the molecular weight of the polyether polymer and the prepolymer, gel permeation chromatography measurement was performed, and the number average molecular weight and the weight average molecular weight were calculated in terms of standard polystyrene. Gel permeation chromatography measurement is performed using a measuring device RID-6A manufactured by Shimadzu Corporation, Showex KD-807, KD-806, KD-806M and KD-803, and a solvent DMF manufactured by Showa Denko K.K. Performed at 60 ° C.

The photoelectric conversion efficiency was measured by adjusting a dye-sensitized solar cell prepared according to the assembly method described below with a sorter simulator YSS-E40 manufactured by Yamashita Denso Co., Ltd. so that the light intensity was 1 Sun, and then TiO ₂ A minus (-) terminal was attached to the pole, and a plus (+) terminal was attached to the counter electrode, and a voltage of -0.1 V to 0.8 V was applied to perform measurement.

式（１a）の、Ａはグリセリン残基である。 [Synthesis Example: Synthesis of Polyether Polymer of Formula (1)]
[Synthesis Example 1]
Synthesis of the polyether polymer of the formula (1a) was performed as follows.
In a three-necked flask, 0.03 mol (3.4 g) of t-butoxy potassium was added to 0.2 mol (18.4 g) of glycerin, and the temperature was raised while stirring. At 120 ° C., n = 1 2-methoxyethylglycidyl of formula (2) 2.5 mol (330.5 g) of ether was added dropwise over 3 hours, and the mixture was heated at 120 ° C. for 3 hours, cooled, and purified.
330 g of a polyether polymer having a skeleton of the following formula (1a) having a number average molecular weight of 2,900 was obtained.

In the formula (1a), A is a glycerin residue.

式（１b）の、Ａはペンタエリスリトール残基である。 [Synthesis Example 2]
Synthesis of the polyether polymer of formula (1b) was carried out as follows.
To a three-necked flask, 0.2 mol (27.2 g) of pentaerythritol was added 0.03 mol (1.7 g) of potassium hydroxide at the end of the differentiation, and the temperature was raised while stirring. At 100 ° C., n = 2 of formula (2) = 2 -(2-Methoxyethoxy) ethoxyglycidyl ether 2.0 mol (352.4 g) was added dropwise over 3 hours, and then heated at 100 ° C. for 3 hours, cooled and purified.
238 g of a polyether polymer having a skeleton of the following formula (1b) having a number average molecular weight of 2,200 was obtained.

In the formula (1b), A is a pentaerythritol residue.

[Example of electrolyte adjustment]
Using 3-methoxypropionitrile as a solvent, 4-t-butylpyridine (0.5M), 1-methyl-3-propylimidazolium iodide (0.6M), iodine (0.03M), guanidine thiocyanate (0.1M) A solution dissolved at a concentration was used as an electrolytic solution.

[Assembly of dye-sensitized solar cells]
The assembly of the dye-sensitized solar cell was performed according to Thin Solid Films 516 (2008) 4613-4619. Specifically, it is as follows.

1) Production of oxide thin film electrode 16 μm of titanium oxide paste having an average particle diameter of 30 nm is applied to a base material (thickness 4 mm, resistance value 30 Ω / cm ² ) made of fluorine-doped tin oxide transparent conductive glass, and further the average particle diameter After applying 4 μm of 400 nm titanium oxide paste, by heating in steps from 325 ° C. to 500 ° C. in an air atmosphere, an oxide thin film electrode made of titanium oxide is formed on the surface of a substrate made of transparent conductive glass did.

2) Manufacture of anode Apply the ethanol solution of chloroplatinic acid prepared to 2 mg / mL to the surface of the base material made of the same transparent conductive glass as that used for the manufacture of the oxide thin film electrode, and then at 400 ° C for 15 minutes. It was formed by heating.

3) Preparation of dye solution A commercially available dye “N719” was dissolved in an acetonitrile / tert-butanol mixed solvent (volume ratio: 50/50) to prepare a dye solution having a dye concentration of 0.5 mmol / L.

4) Manufacture of a cathode The said oxide thin film electrode was immersed in the said pigment | dye solution at room temperature for 20 hours, the pigment | dye was made to adsorb | suck to an oxide thin film electrode, and the cathode was manufactured.

5) Manufacture of dye-sensitized solar cell Arranged so that the platinum sintered surface of the anode and the oxide thin film electrode forming surface of the cathode face each other, are bonded with a sealing material, and a polymer electrolyte solution is injected into the gap Thus, a dye-sensitized solar cell was manufactured.
[Evaluation of dye-sensitized solar cell]
The dye-sensitized solar cells of Examples and Comparative Examples were fitted with a light irradiation area defining mask with a 5 mm square window, and simulated sunlight was irradiated at an illuminance of 100 mW / cm ² using a solar simulator. Irradiation was performed, and the open circuit voltage (hereinafter, Voc), short circuit current (hereinafter, Jsc), fill factor (hereinafter, FF), and photoelectric conversion efficiency were measured.

[Example 1]
A polymer electrolyte was prepared as a solution by adding 0.9 g of the prepared electrolyte to 0.1 g of the polyether polymer obtained in Synthesis Example 1. This solution polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the photoelectric conversion efficiency was measured.
The fill factor FF was 0.61, and the photoelectric conversion efficiency was 7.1%.

[Example 2]
A polymer electrolyte was prepared as a solution by adding 0.9 g of the prepared electrolyte to 0.1 g of the polyether polymer obtained in Synthesis Example 2. This solution polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the photoelectric conversion efficiency was measured.
The fill factor FF was 0.62, and the photoelectric conversion efficiency was 7.3%.

[Example 3]
A polymer electrolyte was prepared by adding 0.9 g of the prepared electrolyte to 0.1 g of the polyether polymer obtained in Synthesis Example 1. To this was added 0.006 g of a crosslinking aid 2,4-tolylene diisocyanate (2,4-TDI) to prepare a polymer electrolyte solution.
This solution-like polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the cell was heated at 80 ° C. for 30 minutes to crosslink and gel the polymer electrolyte, and then the photoelectric conversion efficiency was measured.
The fill factor FF was 0.61, and the photoelectric conversion efficiency was 6.8%.

[Example 4]
A polymer electrolyte was prepared by adding 0.9 g of the prepared electrolyte to 0.1 g of the polyether polymer obtained in Synthesis Example 2. To this was added 0.005 g of a crosslinking aid hexamethylene diisocyanate (HMDI) to prepare a polymer electrolyte solution.
This solution-like polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the cell was heated at 80 ° C. for 30 minutes to crosslink and gel the polymer electrolyte, and then the photoelectric conversion efficiency was measured.
The fill factor FF was 0.61, and the photoelectric conversion efficiency was 7.0%.

[Comparative Example 1]
A polymer electrolyte was prepared in the same manner as in Example 1 except that a polyether polymer having a number average molecular weight of 270,000 obtained by the same method as in [Synthesis Example 1] was used. This solution polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the photoelectric conversion efficiency was measured.
The fill factor FF was 0.58, and the photoelectric conversion efficiency was 4.3%.

[Comparative Example 2]
A polymer electrolyte was prepared in the same manner as in Example 1 except that a commercially available polyacrylonitrile was used instead of the polyether polymer. This solution polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the photoelectric conversion efficiency was measured.
The fill factor FF was 0.58, and the photoelectric conversion efficiency was 1.8%.

[Comparative Example 3]
A polymer electrolyte was prepared in the same manner as in Example 2 except that a polyether polymer having a number average molecular weight of 115,000 obtained by the same method as in [Synthesis Example 1] was used. To this, 0.001 g of a crosslinking aid 2,4-tolylene diisocyanate (2,4-TDI) was added to prepare a polymer electrolyte solution.
This solution-like polymer electrolyte was injected into the assembled dye-sensitized solar cell, and the cell was heated at 80 ° C. for 30 minutes to crosslink and gel the polymer electrolyte, and then the photoelectric conversion efficiency was measured.
The fill factor FF was 0.57, and the photoelectric conversion efficiency was 4.0%.

The results of the above examples and comparative examples are shown in Table 1.

  The composition for polymer solid electrolytes of the present invention can be used for dye-sensitized solar cells.

Claims (7)

(i) a glycidyl ether polymer represented by formula (1) (when n = 0) or a polyether polymer having an oxyethylene unit in the side chain (when n ≠ 0);

[Wherein, A is an active hydrogen-containing compound residue, R is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl having 6 to 14 carbon atoms. And at least one group selected from the group of aralkyl groups having 7 to 12 carbon atoms. M represents an integer of 1 to 1,200, n represents an integer of 0 to 25, and p represents an integer of 1 to 12, respectively. ]
(ii) an electrolyte containing a redox couple,
A polymer electrolyte composition for a dye-sensitized solar cell, comprising:   The polymer electrolyte composition for a dye-sensitized solar cell according to claim 1, further comprising (iii) at least one crosslinking agent selected from compounds having two or more isocyanate groups.   Item 3. The polymer electrolyte composition for a dye-sensitized solar cell according to Item 1 or 2, wherein the active hydrogen-containing compound residue A is derived from a polyhydric alcohol.   The crosslinking agent is 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI) ), Isophorone diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylolpropane TDI 3 molar adduct or these The polymer electrolyte composition for a dye-sensitized solar cell according to claim 2 or 3, wherein the polymer electrolyte composition is at least one selected from the group consisting of any mixture of the following.   The polymer electrolyte composition for a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the redox pair is a pair of iodine and iodine compound or bromine and bromine compound.   The polymer electrolyte composition for a dye-sensitized solar cell according to any one of claims 1 to 5, wherein the electrolytic solution is an aprotic organic solvent. The dye-sensitized solar cell using the polymer electrolyte composition for dye-sensitized solar cells in any one of Claims 1-6.