JP2004281267A - Electrolyte for dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte for a dye-sensitized solar cell that can gel without needs for operations such as heat-treatment affecting cell elements including the electrolyte. <P>SOLUTION: The liquid electrolyte contains a redox material and a siloxane-modified acrylic polymer. The liquid electrolyte is left in the air and allowed to gel on a dye absorbing semiconductor film to form an electrolyte gel. Alternatively, the liquid electrolyte contains a redox material, a siloxane-modified acrylic polymer and an aminosilane, and is encapsulated in a cell of the solar cell and allowed to gel to form an electrolyte gel. The dye-sensitized solar cell has the electrolyte 6 between dye-sensitized semiconductor electrodes 2, 3 and a counter-electrode 4 disposed facing the electrodes 2, 3. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５４】
表１及び図２より、本発明のゲル状電解質は、従来の液状電解質よりは若干劣るものの優れた電池性能を示すことが明らかである。
【００５５】
実施例２
実施例１で用いたものと同様の酸化還元性物質溶液０．４ｇに、シロキサン変性アクリル２０重量％溶液０．１ｇとアミノシランのアセトニトリル溶液（アミノシラン濃度２０重量％）０．１ｇとを添加して、密閉ゲル化型の液状電解質を調製した。
【００５６】
この液状電解質を用い、これを色素増感型導電体電極と対向電極との間に封止したこと以外は実施例１と同様にして色素増感型太陽電池を作製し（即ち、注入口のみを残して、予め組み立てたセル状に液状電解質を封入した後、封止した。）、液状電解質のゲル化が進行していない密封初期及び液状電解質がゲル化した密閉６日後の色素増感型太陽電池について、各々、同様に評価を行って、結果を表２及び図３に示した。なお、表２及び図３には比較例１の結果を併記した。
【００５７】
【表２】

【００５８】
表２及び図３より、本発明のゲル状電解質は、従来の液状電解質とほぼ同等の電池性能を示し、特に、密閉状態でのゲル化の過程においても初期性能が維持され、ゲル化による性能低下は殆どないことが分かる。
【００５９】
【発明の効果】
以上詳述した通り、本発明によれば、電解質、その他の電池要素に影響を及ぼすことなくゲル化可能な色素増感型太陽電池用電解質により、電解質を容易にゲル化することにより凝固体化して、その液漏れを防止することができ、発電効率、耐久性、信頼性、安全性に優れた色素増感型太陽電池を提供することができる。
【図面の簡単な説明】
【図１】色素増感型太陽電池の一般的な構造を示す断面図である。
【図２】実施例１及び比較例１の電圧−電流密度曲線のグラフである。
【図３】実施例２及び比較例１の電圧−電流密度曲線のグラフである。
【符号の説明】
１ 基板
２ 透明電極
３ 色素吸着半導体膜
４ 対向電極
５ 封止材
６ 電解質[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a dye-sensitized solar cell electrolyte and a dye-sensitized solar cell, and more particularly to a gel electrolyte used for a dye-sensitized solar cell, and a dye-sensitized solar cell including such a gel electrolyte. About.
[0002]
[Prior art]
It is already known to form a solar cell using an oxide semiconductor to which a sensitizing dye is adsorbed as an electrode. FIG. 1 is a cross-sectional view showing a general structure of such a dye-sensitized solar cell. As shown in FIG. 1, a transparent electrode 2 is provided on a substrate 1 such as a glass substrate, and a metal oxide semiconductor film 3 having a spectral sensitizing dye adsorbed thereon is formed on the transparent electrode 2. A counter electrode 4 is provided at a distance from the transparent electrode 2 of the dye-sensitized semiconductor electrode, and the side portion is sealed with a sealing material 5. 4 and an electrolyte 6 is sealed. The dye-adsorbing semiconductor film 3 is usually made of a titanium oxide thin film on which a dye is adsorbed, and the dye adsorbed on the titanium oxide thin film is excited by visible light, and the generated electrons are passed to the titanium oxide fine particles to generate power. Done.
[0003]
[Problems to be solved by the invention]
Conventionally, the electrolyte of a dye-sensitized solar cell is generally a liquid electrolyte obtained by dissolving an oxidation-reduction substance in a solvent, and thus has a problem such as liquid leakage from a sealing portion. This affected the durability and reliability of the solar cell.
[0004]
In order to solve this problem, conventionally, it has been studied to make the liquid electrolyte into a gel state to make it quasi-solid.
[0005]
Conventionally, as a general gelling means, a method of causing a polymerization initiator such as a peroxide to act on various gelling monomers to perform radical polymerization has been known, but iodine contained as an oxidation-reduction substance in an electrolyte is known. In addition, this method cannot be used for gelling the electrolyte because polymerization by peroxide is inhibited. On the other hand, there is also a method in which an acrylic monomer is used as a gelling monomer and heat polymerization is carried out in the presence of a polymerization initiator. Specifically, a dye-adsorbed semiconductor film (for example, a titanium oxide thin film on which a dye is adsorbed) is used. Above, a gel electrolyte is formed by heating and polymerizing a gelling electrolyte solution containing a redox substance, an acrylic monomer, and a polymerization initiator. However, in this method, a heat treatment at about 80 ° C. needs to be performed on the dye-adsorbed semiconductor film for several hours for heat polymerization, while the heat resistance of the dye adsorbed on the dye-adsorbed semiconductor film is at most 80 ° C. The heat treatment at the heat-resistant limit deteriorates the dye of the dye-adsorbed semiconductor film, and as a result, there is a problem that the conversion efficiency of the solar cell is reduced. Further, such a heat treatment is not preferable in that it also changes the composition of the electrolyte forming solution.
[0006]
The present invention solves the above-described conventional problems, and does not require an operation such as heat treatment that affects the electrolyte and other battery elements, and is capable of gelling and dye-sensitized solar cell electrolyte. An object is to provide a dye-sensitized solar cell using an electrolyte for a dye-sensitized solar cell.
[0007]
[Means for Solving the Problems]
The liquid electrolyte for a dye-sensitized solar cell of the present invention is characterized by containing a redox substance and a siloxane-modified acryl-based polymer.
[0008]
The present inventors have conducted intensive studies on the gelation of the electrolyte. As a result, if the acrylic polymer is a siloxane-modified product (hereinafter sometimes referred to as “siloxane-modified acrylic”), iodine that inhibits the radical polymerization reaction It has been found that, even in an electrolyte containing, a gel is formed by absorbing and polymerizing the moisture in the air, and furthermore, a gel is formed even in a closed state due to the coexistence of aminosilane, thereby completing the present invention.
[0009]
That is, in the siloxane-modified acrylic, the introduced siloxane unit reacts with atmospheric moisture (H ₂ O) to condense at this portion and gel. When aminosilane coexists, the siloxane unit reacts with aminosilane to condense at this portion and gel. Alternatively, it is presumed that aminosilane promotes the self-condensation reaction.
[0010]
In the present invention, the liquid electrolyte for a dye-sensitized solar cell containing an oxidation-reduction substance and a siloxane-modified acrylic is obtained by dissolving an oxidation-reduction substance and a siloxane-modified acrylic in a solvent. Is preferably 0.1 to 20 mol / L, and the content of the siloxane-modified acrylic is preferably 1 to 20% by weight.
[0011]
Further, a liquid electrolyte for a dye-sensitized solar cell containing an oxidation-reduction substance, a siloxane-modified acrylic, and an aminosilane is obtained by dissolving an oxidation-reduction substance, a siloxane-modified acrylic, and an aminosilane in a solvent. It is preferable that the content is 0.1 to 20 mol / L, the content of the siloxane-modified acrylic is 1 to 20% by weight, and the content of the aminosilane is 30 to 80% by weight based on the siloxane-modified acrylic.
[0012]
The gel electrolyte for a dye-sensitized solar cell of the present invention is obtained by gelling such a liquid electrolyte for a dye-sensitized solar cell of the present invention. That is, the gel electrolyte of the present invention is preferably obtained by leaving a liquid electrolyte for a dye-sensitized solar cell containing an oxidation-reduction substance and a siloxane-modified acrylic in the air, preferably on a dye-adsorbed semiconductor film. In this case, the liquid electrolyte containing the redox substance, the siloxane-modified acrylic, and the aminosilane is gelled in a hermetically sealed state, preferably in a state of being sealed in a solar cell.
[0013]
The dye-sensitized solar cell of the present invention includes a dye-sensitized semiconductor electrode, a counter electrode provided to face the dye-sensitized semiconductor electrode, and a gap between the dye-sensitized semiconductor electrode and the counter electrode. A dye-sensitized solar cell having an electrolyte disposed therein, wherein the electrolyte is such a gel-type electrolyte for a dye-sensitized solar cell of the present invention, or a dye-sensitized gelable electrolyte in a sealed state. It is a liquid electrolyte for sensitive solar cells.The electrolyte can be gelled without affecting the electrolyte and other battery elements. Excellent in efficiency, durability, reliability and safety.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the electrolyte for a dye-sensitized solar cell and the dye-sensitized solar cell of the present invention will be described in detail.
[0015]
First, a siloxane-modified acrylic as a gelling agent in the present invention will be described.
[0016]
The siloxane-modified acrylic is obtained by modifying an acrylic polymer (including a copolymer) by introducing siloxane, and the acrylic monomer constituting the main-chain acrylic polymer includes methyl methacrylate, One or more of ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methyl methacrylate and the like, preferably methyl methacrylate and the like.
[0017]
If the molecular weight of the acrylic polymer is too small, it is difficult to gel, whereas if it is too large, the viscosity of the electrolyte solution becomes high, making it difficult to penetrate into the pores of the titanium oxide film, and making it difficult for ions to move. Battery performance decreases. However, an oligomer having a molecular weight of about 360 to 80,000 is preferable because the higher the molecular weight, the more easily the gelation occurs.
[0018]
Examples of the siloxane unit to be introduced into such an acrylic polymer include those represented by (RO) ₃ SiO—, where R is an alkyl group such as a methyl group or an ethyl group, preferably methyl Group.
[0019]
If the amount of the siloxane unit introduced is too small, the condensation reaction by the siloxane unit is insufficient, and the gelation does not proceed sufficiently. On the other hand, if the amount of the siloxane unit introduced is excessively large, the hydrophobicity becomes strong, it becomes difficult to penetrate into the pores of titanium oxide, and the battery performance deteriorates. Therefore, the ratio of siloxane (RO) ₃ SiO to the acrylic group is 1 to 50. It is preferable that the amount is about% by weight.
[0020]
Further, as the aminosilane used in combination with such a siloxane-modified acrylic, a substance called an amino-based silane coupling agent can be used, and examples thereof include the following.
[0021]
3-acryloxypropyltrimethoxysilane:
(CH ₃ O) ₃ SiC ₃ H ₆ OCOCH = CH ₂
N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane:
(CH ₃ O) ₂ Si (CH ₃ ) C ₃ H ₆ NHC ₂ H ₄ NH ₂
N-2 (aminoethyl) 3-aminopropyltrimethoxysilane:
(CH ₃ ) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH ₂
N-2 (aminoethyl) 3-aminopropyltriethoxysilane:
(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH _{2
3-aminopropyltrimethoxysilane: (CH 3 O) 3 SiC} 3 H 6 NH 2
3-Aminopropyltriethoxysilane:
(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂
3-triethoxysilyl-N-(1,3-dimethyl - butylidene) _{propylamine: (C 2 H 5 O)} SiC 3 H 6 N = C (CH 3) C 4 H 9
N-phenyl-3-aminopropyltrimethoxysilane:
(CH ₃ O) ₃ SiC ₃ H ₆ NH (Ph)
[0022]
The redox substance is not particularly limited as long as it can be generally used in a battery or a solar cell. LiI, NaI, KI, a combination of metal iodide such as CaI ₂ and iodine, LiBr, NaBr, A combination of a metal bromide such as KBr and CaBr ₂ with bromine is preferred, and among these, a combination of a metal iodide and iodine is preferred.
[0023]
The liquid electrolyte for a dye-sensitized solar cell of the present invention is prepared by dissolving a redox substance and siloxane-modified acrylic, or a redox substance, siloxane-modified acrylic, and aminosilane in a solvent.
[0024]
Examples of the solvent include carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol, and one or more kinds of water, aprotic polar substances, and the like. Compounds and nitrile compounds are preferred.
[0025]
When the liquid electrolyte for a dye-sensitized solar cell of the present invention is a gel electrolyte liquid electrolyte containing an oxidation-reduction substance and a siloxane-modified acrylic, the content of the oxidation-reduction substance is 0.1 to 20. It is preferable that the content of the siloxane-modified acrylic is 1 to 20% by weight in mol / L. When the content of the redox substance is less than 0.1 mol / L, sufficient power generation efficiency cannot be obtained, and when it exceeds 20 mol / L, the viscosity of the electrolyte solution becomes high, which is not suitable. The preferred content of the redox substance is 0.3 to 15 mol / L. On the other hand, if the content of the siloxane-modified acrylic is less than 1% by weight, sufficient gelation does not occur, and if it exceeds 20% by weight, the hydrophobicity becomes strong, it becomes difficult to penetrate into the titanium oxide pores, and the battery performance deteriorates. The preferred content of the siloxane-modified acrylic is 2 to 15% by weight.
[0026]
When the liquid electrolyte for a dye-sensitized solar cell of the present invention is a sealed gelled liquid electrolyte containing an oxidation-reduction substance, a siloxane-modified acrylic, and an aminosilane, the content of the oxidation-reduction substance is 0.1 to 0.1%. It is preferable that the content of the siloxane-modified acrylic is 20 to 20% by weight at 20 mol / L, and the content of the aminosilane is 30 to 80% by weight based on the siloxane-modified acrylic. When the content of the redox substance is less than 0.1 mol / L, sufficient power generation efficiency cannot be obtained, and when it exceeds 20 mol / L, the viscosity of the electrolyte solution becomes high, which is not suitable. The preferred content of the redox substance is 0.3 to 15 mol / L. On the other hand, if the content of the siloxane-modified acrylic is less than 1% by weight, sufficient gelation does not occur. Is difficult to move, and the battery performance is reduced. The preferred content of the siloxane-modified acrylic is 2 to 15% by weight. On the other hand, if the content of aminosilane is less than 30% by weight based on the siloxane-modified acrylic, sufficient gelation does not occur, and if it exceeds 80% by weight, a hard solid is formed, and the battery performance deteriorates, which is not suitable. The preferred aminosilane content is 40-70% by weight.
[0027]
An air-released gel electrolyte containing an oxidation-reduction substance and a siloxane-modified acrylic can be gelled with atmospheric moisture by leaving it in the air. In this case, it is preferable to prepare a dye-adsorbing semiconductor film described later, provide a weir with a frame material or the like on the dye-adsorbing semiconductor film, and arrange a liquid electrolyte on the dye-adsorbing semiconductor film so as to have a predetermined thickness. It may be left in the atmosphere as it is. The conditions for leaving in the air may be room temperature, and the leaving time for the gelation may vary depending on the composition and liquid amount of the liquid electrolyte, but is usually about 1 to 3 days.
[0028]
A solar cell may be assembled using a gel electrolyte film formed on the dye-adsorbed semiconductor film in this manner.
[0029]
A sealed gelled liquid electrolyte containing a redox substance, siloxane-modified acrylic, and aminosilane can be used by directly encapsulating it in a solar cell, and this liquid electrolyte can be used over time in the sealed state. Gels. This standing temperature may be room temperature, and the time required for gelation varies depending on the composition and liquid amount of the liquid electrolyte, but is usually about 1 to 3 days.
[0030]
Since the thickness of the electrolyte of the dye-sensitized solar cell is usually about 10 nm to 2 mm, the gel electrolyte of the present invention is preferably gelled to have such a thickness.
[0031]
The dye-sensitized solar cell of the present invention uses such an electrolyte for a dye-sensitized solar cell of the present invention as an electrolyte. Has the same configuration as the above dye-sensitized solar cell.
[0032]
The substrate 1 of the dye-sensitized solar cell is usually a glass plate, and is usually a silicate glass, but various plastic substrates and the like can be used as long as visible light transmittance can be ensured. The thickness of the substrate is generally 0.1 to 10 mm, preferably 0.3 to 5 mm. The glass plate is preferably chemically or thermally strengthened.
[0033]
As the transparent electrode 2, a substrate formed of a conductive metal oxide thin film of In ₂ O ₃ or SnO ₂ or a substrate made of a conductive material such as a metal is used. Preferred examples of the conductive metal oxide include In ₂ O ₃ : Sn (ITO), SnO ₂ : Sb, SnO ₂ : F, ZnO: Al, ZnO: F, and CdSnO ₄ .
[0034]
Examples of the metal oxide semiconductor of the metal oxide semiconductor film 3 to which the spectral sensitizing dye has been adsorbed include titanium oxide, zinc oxide, tungsten oxide, antimony oxide, niobium oxide, tungsten oxide, indium oxide, barium titanate, and strontium titanate. And one or more known semiconductors such as cadmium sulfide and the like. Particularly, titanium oxide is preferable from the viewpoint of stability and safety. Examples of titanium oxide include various titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, and orthotitanic acid, or titanium hydroxide, and hydrated titanium oxide. Titanium oxide is preferred. Further, the metal oxide semiconductor film preferably has a fine crystal structure. It is also preferable that the film is a porous film. The thickness of the metal oxide semiconductor is generally 1 to 20 μm or more, preferably 5 to 15 μm.
[0035]
The organic dye (spectral sensitizing dye) to be adsorbed to the oxide semiconductor film has an absorption in a visible light region and / or an infrared light region, and one or more of various metal complexes and organic dyes are used. Can be used. Spectral sensitizing dyes having a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, or a carboxyalkyl group in the molecule are preferred because of their quick adsorption to semiconductors. Further, a metal complex is preferred because of its excellent spectral sensitizing effect and durability. As the metal complex, a metal phthalocyanine such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll, hemin, and a complex of ruthenium, osmium, iron, and zinc described in JP-A-1-220380 and JP-A-5-504033 are used. Can be. As the organic dye, metal free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, and triphenylmethane dye can be used. Specific examples of the cyanine dye include NK1194 and NK3422 (both manufactured by Japan Photographic Dye Laboratories). Specific examples of the merocyanine dye include NK2426 and NK2501 (both manufactured by Japan Photographic Dye Laboratories). Specific examples of xanthene dyes include uranine, eosin, rose bengal, rhodamine B, and dibromofluorescein. Specific examples of the triphenylmethane dye include malachite green and crystal violet.
[0036]
The organic dye (spectral sensitizing dye) is adsorbed on the semiconductor film. To this end, the oxide semiconductor film is immersed in the organic dye solution prepared by dissolving the organic dye in an organic solvent at room temperature or under heating. Just do it. As a solvent for the above solution, any solvent may be used as long as it dissolves the spectral sensitizing dye to be used, and specifically, water, alcohol, toluene, and dimethylformamide can be used.
[0037]
Further, any material having conductivity may be used as the counter electrode 4, and any conductive material may be used. The reduction reaction of oxidized redox ions such as I ₃ ⁻ ions of the electrolyte can be performed at a sufficient speed. It is preferable to use one having a catalytic ability to be carried out. Examples of such a material include a platinum electrode, a material obtained by subjecting a conductive material to platinum plating or platinum deposition, rhodium metal, ruthenium metal, ruthenium oxide, carbon, cobalt, nickel, chromium, and the like.
[0038]
The dye-sensitized semiconductor electrode is formed by coating a transparent electrode (transparent conductive film) 2 on a substrate 1, forming a photoelectric conversion material semiconductor film thereon, and adsorbing the dye as described above. You.
[0039]
In the case of the above-mentioned gel electrolyte liquid electrolyte which is open to the atmosphere, a gel electrolyte membrane is formed by gelation to the air on the semiconductor film on which the dye of the semiconductor electrode is adsorbed, and the semiconductor formed with the gel electrolyte membrane A solar cell can be obtained by stacking a substrate such as a glass plate coated with another transparent conductive film as an opposite electrode on the electrode.
[0040]
In the case of the aforementioned sealed gelled liquid electrolyte, a substrate such as a glass plate coated with another transparent conductive film as the counter electrode 4 faces the above-mentioned dye-sensitized semiconductor electrode, and The liquid electrolyte may be gelled over time while being sealed in the solar cell. By gelling in a sealed state in this manner, problems such as a change in the composition and deterioration of the electrolyte during the gelation process can be prevented, and the initial performance can be kept high.
[0041]
In the dye-sensitized solar cell of the present invention, the dye-sensitized semiconductor electrode, the electrolyte and the counter electrode are housed and sealed in a case, but may be entirely resin-sealed. In this case, the dye-sensitized semiconductor electrode has a structure in which light is applied. In a battery having such a structure, when sunlight or visible light equivalent to sunlight is applied to the dye-sensitized semiconductor electrode, a potential difference is generated between the dye-sensitized semiconductor electrode and its counter electrode, and the voltage between the two electrodes is increased. The current starts to flow.
[0042]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples as long as the gist is not exceeded.
[0043]
In the following, the following was used as the siloxane-modified acrylic and aminosilane.
[0044]
[Siloxane modified acrylic]
Dainippon Ink and Chemicals Co., Ltd. "HARDIC" (relative to methyl methacrylate oligomer unit _{(CH 3} O) 3 SiO- which group is introduced about 5 wt%. Molecular weight of about 60,000 (Mw))
[Aminosilane]
3-aminopropyltrimethoxysilane
Example 1
0.1 g of a 20% by weight solution of siloxane-modified acrylic (isopropanol) was added to 0.4 g of a redox substance solution having the following composition to prepare a liquid electrolyte which was open to the atmosphere.
[0046]
[Redox substance solution]
Solvent (acetonitrile)
Lithium iodide: 0.1 mol / L
1,2-dimethyl-3-propylimidazolium iodide: 0.15 mol / L
Iodine: 0.04 mol / L
t-butylpyridine: 0.4 mol / L
[0047]
Using this liquid electrolyte, a dye-sensitized solar cell was manufactured as follows.
[0048]
A FTO (fluorine-doped tin oxide) film having a thickness of 9000 mm is formed on a glass substrate (thickness: 2 mm), a titanium oxide film having a thickness of 10 μm is applied thereon, dried, and then heated at 450 ° C. for 30 minutes. Fired.
[0049]
As a spectral sensitizing dye, cis-di (thiocyanato) -bis (2,2′-bipyridyl-4-dicarboxylate-4′-tetrabutylammonium carboxylate) ruthenium (II) was added to an ethanol solution at 3 × 10 ^−4. The substrate on which the titanium oxide film was formed was put into a solution dissolved at mol / L, and immersed at room temperature for 18 hours to obtain a dye-sensitized semiconductor electrode. The adsorption amount of the spectral sensitizing dye was 10 μg per 1 cm ² of the specific surface area of the titanium oxide film.
[0050]
A liquid flow prevention tape is attached to the dye-sensitized semiconductor electrode to form a weir. The liquid electrolyte is coated and impregnated, and left standing at room temperature for 6 hours in the air to form a gel. Was formed. On the surface of the electrolyte membrane, a transparent conductive glass plate carrying platinum was laminated as a counter electrode, and after sealing the side surface with a resin, a lead wire was attached to produce a dye-sensitized solar cell of the present invention. .
[0051]
When the obtained dye-sensitized solar cell was irradiated with light of 100 mW intensity (cell area 1 cm ² ) using a solar simulator, the Isc current (7.4 mA current) and Eff conversion efficiency (2.84) were shown in Table 1. And the voltage-current density curve was as shown in FIG.
[0052]
Comparative Example 1
A dye was prepared in the same manner as in Example 1 except that only a redox substance solution containing no siloxane-modified acrylic was used as a liquid electrolyte, and this was sealed between a dye-sensitized conductor electrode and a counter electrode. A sensitized solar cell was manufactured and similarly evaluated, and the results are shown in Table 1 and FIG.
[0053]
[Table 1]

[0054]
From Table 1 and FIG. 2, it is clear that the gel electrolyte of the present invention exhibits excellent battery performance although slightly inferior to the conventional liquid electrolyte.
[0055]
Example 2
To 0.4 g of the same redox substance solution as used in Example 1, 0.1 g of a siloxane-modified acrylic 20% by weight solution and 0.1 g of an aminosilane acetonitrile solution (aminosilane concentration 20% by weight) were added. A sealed gelled liquid electrolyte was prepared.
[0056]
Using this liquid electrolyte, a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the liquid electrolyte was sealed between the dye-sensitized conductor electrode and the counter electrode (that is, only the injection port was used). The liquid electrolyte was sealed in a pre-assembled cell shape, and sealed.), And the dye-sensitized type at the initial stage of sealing when the gelling of the liquid electrolyte did not proceed and at 6 days after sealing when the liquid electrolyte gelled. Each of the solar cells was similarly evaluated, and the results are shown in Table 2 and FIG. Table 2 and FIG. 3 also show the results of Comparative Example 1.
[0057]
[Table 2]

[0058]
From Table 2 and FIG. 3, the gel electrolyte of the present invention shows almost the same battery performance as the conventional liquid electrolyte. In particular, even in the process of gelation in a closed state, the initial performance is maintained, and the performance due to gelation is maintained. It can be seen that there is almost no decrease.
[0059]
【The invention's effect】
As described in detail above, according to the present invention, the electrolyte is easily solidified by the gelation of the electrolyte by the dye-sensitized solar cell electrolyte that can be gelled without affecting other battery elements. As a result, the liquid leakage can be prevented, and a dye-sensitized solar cell excellent in power generation efficiency, durability, reliability, and safety can be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a general structure of a dye-sensitized solar cell.
FIG. 2 is a graph of a voltage-current density curve of Example 1 and Comparative Example 1.
FIG. 3 is a graph of a voltage-current density curve of Example 2 and Comparative Example 1.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Substrate 2 Transparent electrode 3 Dye adsorption semiconductor film 4 Counter electrode 5 Sealing material 6 Electrolyte

Claims (11)

A liquid electrolyte for a dye-sensitized solar cell, comprising: a redox substance; and a siloxane-modified acrylic polymer. 2. The acrylic resin according to claim 1, wherein a redox substance and a siloxane-modified acrylic polymer are dissolved in a solvent, and the content of the redox substance is 0.1 to 20 mol / L. A liquid electrolyte for a dye-sensitized solar cell, wherein the content of the siloxane-modified polymer is 1 to 20% by weight. 2. The liquid electrolyte for a dye-sensitized solar cell according to claim 1, further comprising an aminosilane. 4. The method according to claim 3, wherein the oxidation-reduction substance, the siloxane-modified acryl polymer, and aminosilane are dissolved in a solvent, and the content of the oxidation-reduction substance is 0.1 to 20 mol / L. A dye characterized in that the content of the modified siloxane of the acrylic polymer is 1 to 50% by weight, and the content of the aminosilane is 30 to 80% by weight based on the modified siloxane of the acrylic polymer. Liquid electrolyte for sensitized solar cells. A gel electrolyte for a dye-sensitized solar cell, which is obtained by gelling the liquid electrolyte for a dye-sensitized solar cell according to any one of claims 1 to 4. A gel electrolyte for a dye-sensitized solar cell, wherein the liquid electrolyte for a dye-sensitized solar cell according to claim 1 or 2 is gelled by being left in the atmosphere. 7. The gel electrolyte for a dye-sensitized solar cell according to claim 6, wherein the liquid electrolyte for a dye-sensitized solar cell is left on a dye-adsorbed semiconductor film to be gelled. A gel electrolyte for a dye-sensitized solar cell, wherein the liquid electrolyte for a dye-sensitized solar cell according to claim 3 or 4 is gelled in a sealed state. 9. The gel electrolyte for a dye-sensitized solar cell according to claim 8, wherein the liquid electrolyte for a dye-sensitized solar cell is sealed in a solar cell and then gelled. Dye-sensitization comprising a dye-sensitized semiconductor electrode, a counter electrode provided to face the dye-sensitized semiconductor electrode, and an electrolyte disposed between the dye-sensitized semiconductor electrode and the counter electrode. A dye-sensitized solar cell, wherein the electrolyte is the liquid electrolyte for a dye-sensitized solar cell according to claim 3. Dye-sensitization comprising a dye-sensitized semiconductor electrode, a counter electrode provided to face the dye-sensitized semiconductor electrode, and an electrolyte disposed between the dye-sensitized semiconductor electrode and the counter electrode. A dye-sensitized solar cell, wherein the electrolyte is the gel electrolyte for a dye-sensitized solar cell according to any one of claims 5 to 9.

Images