JP2005056613A - Dye sensitized solar battery and module thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost dye sensitized solar battery that prevents corrosion by electrolyte from occurring easily even if using ITO and a base metal in an electron transportation layer and has satisfactory performance retainability and superior durability. <P>SOLUTION: In the dye sensitized solar battery, a collective electrode, a photoelectric conversion layer allowing dye to be adsorbed to a porous semiconductor layer, a carrier transportation layer, and a counter electrode are successively laminated between first and second supports from the first support side, where at least one of them is made of a light transmitting material from a first support side. In the counter electrode, the electron transportation layer for transporting electrons, a corrosion prevention layer, and a catalyst layer made of a catalyst material, are successively laminated from the second support side. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００４７】
図４で、試料１Ａのガラス基板１２上のアルミニウム薄板１３で覆われていない部分に２つの穴をあけた。
熱融着フィルム（三井・デュポンポリケミカル株式会社製、商品名ハイミラン１６５２）を試料１Ｂの酸化チタン膜（図示せず）の周囲に配設し、試料１Ｂのガラス板と穴の開いた試料１Ａのガラス板をクリップで挟み、１００℃、３０分間、加熱し、熱融着フィルム（図示せず）を接着させた。その外側を、エポキシ封止材で封止した。
【００４８】
得られた試料のガラス基板１２の一方の穴から酸化還元性電解液（ＤＭＰＩＩ（ジメチルプロピルイミダゾールアイオダイド）：０．６モル／リトッルｉＩ：０．１ｍｏｌ、Ｉ_２：０．１ｍｏｌ、ＴＢＰ（ターシャルブチルピリジン）：０．５ｍｏｌ、溶媒：アセトニトリル）を注入し、それらの穴にガラスビーズを入れ、エポキシ封止材８にて封止をおこなった。この電解液が、キャリア輸送層４となり、図１の色素増感太陽電池１Ｄを得た。
【００４９】
図１に示す本発明の色素増感太陽電池１Ｄに、ソーラーシミュレーター（ワコム社製）を用いて、強度１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、変換効率６．２％であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、変換効率６．２％であった。
【００５０】
（実施例２）
図３は、本発明の色素増感太陽電池の対極の電子輸送層として、アルミニウム薄板を用いた場合の断面図である。アルミニウム薄板１３を３ｃｍ×１．６ｃｍに切断し、スパッターによりＰｔをアルミニウム薄板１３上に堆積し、Ｐｔ膜１４を形成する。これを実施例１に準じて沸騰水処理を行い、対極１６を作製して（図３参照）、得られた対極１６をガラス基板１２（Ｃｏｒｎｉｎｇ社製 コード番号７０５９ 形状４ｃｍ×１０．２ｃｍ×０．１１ｃｍ）上に、作製した対極１６のＰｔが堆積していない面に接着剤２４を薄く塗布、乾燥した後、接着させる。
図５は、本発明の色素増感太陽電池の対極のパターン図２Ａである。図５に示すａの長さは０．１ｃｍ、ｂの長さが０．５ｃｍ、ｃの長さが０．４ｃｍである。この対極１６を接着させたガラス基板１２を試料２Ａとする。
【００５１】
図６は、本発明の色素増感太陽電池の酸化チタン膜のパターン図２Ｂである。酸化チタン膜１７を１ｃｍ×３ｃｍのパターンで、あらかじめレーザースクライブにより、透明導電膜の一部を除去した（スクライブ部：１８）透明導電膜つきガラス基板１９上に、図６に示すとおり塗布した。図６に示すｄの長さは１ｃｍ、ｅの長さは０．８ｃｍである。電気炉（デンケン株式会社製、製品名：ＫＤＦ−ＥＳ７２）を用いて、５００℃で１時間焼成した。焼成後の酸化チタン膜１４の膜厚は２０μｍであった。これを試料２Ｂとする。
実施例１に準じて色素吸着を行い、得られた試料を試料２Ｃとする。
【００５２】
図７は、本発明の色素増感太陽電池の、ガラス基板に酸化チタン膜を配設した試料の上に配設した封止材料、絶縁層のパターン図２Ｃである。図７に示すように、熱融着フィルム（三井・デュポンポリケミカル株式会社製、商品名ハイミラン１６５２、厚み５０μｍ、幅０．２ｃｍ）２０を、ｆが０．２ｃｍ、ｇが０．４ｃｍとなるように試料２Ｃの周囲に配設する。対極１６と透明導電膜付ガラス基板１９とを接続する導電層（銀微粒子４５μｍ：チタン微粒子０．５μｍ：ポリマー状シリコンマトリックス＝１：１０：４の重量比を持つ混合材料）２１をｈが０．４ｃｍとなるように、酸化チタン１７の間に配設する。図中、１８はスクライブ部を示す。
【００５３】
試料２Ａに、熱融着フィルム２０と導電層２１で囲まれた一区画あたりに２つの穴を対極部以外に穴を開けた。この試料２Ａを試料２Ｃの図７に示したｇの部分が４ｍｍ程度熱融着フィルムの外側に出るように設置した。試料２Ｃのガラス板と穴の開いた試料２Ａのガラス板をクリップで挟み、１００℃、３０分間、加熱し、熱融着フィルム２０と導電層２１を接着させた。その外側を、エポキシ封止材２３で封止した。
【００５４】
図８は色素増感太陽電池モジュール２Ｄの概略断面図である。得られた試料のガラス基板１２の一方の穴から酸化還元性電解液２２（ＤＭＰＩＩを０．６モル／リトッルｉＩを０．１ｍｏｌ、Ｉ_２を０．１ｍｏｌ、ＴＢＰを０．５ｍｏｌ、溶媒：アセトニトリル）を注入し、全ての穴にガラスビーズを入れ、エポキシ封止材にて、封止を行うことにより色素増感太陽電池モジュール２Ｄを作製した（図８参照）。図中、１９０はガラス基板を、１９１は透明導電膜を示す。
【００５５】
図８に示す本発明の色素増感太陽電池モジュール２Ｄに、ソーラーシミュレーター（ワコム社製）を用いて、強度１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、電流密度：１２．８ｍＡ／ｃｍ^２、開放電圧：３．１Ｖ、ＦＦ：０．５５２であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、電流密度：１２．６ｍＡ／ｃｍ^２、開放電圧：３．２Ｖ、ＦＦ：０．５５５であった。
【００５６】
（実施例３）
図９は、本発明の色素増感太陽電池モジュール３Ｄの概略断面図である。アルミニウム薄板１３上に、該アルミニウム薄板１３の長辺の片側の０．２ｃｍ×３ｃｍ部分に白金膜１４が堆積しないようにマスクで覆ったうえで、スパッターで白金を堆積し、アルミニウム薄板１３と導電層２１とが図８のように直接接触させる以外は、実施例２に準じて作製を行い、得られた色素増感太陽電池モジュール３Ｄとした。
【００５７】
得られた色素増感太陽電池モジュール３Ｄに、ソーラーシミュレーター（ワコム社製）を用いて、強度１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、電流密度：１３ｍＡ／ｃｍ^２、開放電圧：３．１Ｖ、ＦＦ：０．６０２であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、電流密度：１２．７ｍＡ／ｃｍ^２、開放電圧：３．２Ｖ、ＦＦ：０．６０３であった。
【００５８】
実施例３で作製した色素増感太陽電池モジュール３Ｄは、実施例２で作製した色素増感太陽電池モジュール２Ｄと比較して、対極１６と導電層２１の接触部分が、アルミニウム薄板１３と導電層２１とが直接接触しているため、ＦＦが高くなっている。
よって、実施例３に示した本発明の色素増感太陽電池モジュール３ＤはＦＦが高いことが確認できた。
【００５９】
（比較例１）
Ｐｔを堆積させたアルミニウム薄板に沸騰水処理を行わないこと以外は、実施例１に準じて作製を行った。
得られた色素増感太陽電池モジュールＨ１Ｄにソーラーシミュレーター（ワコム社製）を用いて、強度１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、変換効率５．７％であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、変換効率０Ｖであった。
【００６０】
実施例１では一ヶ月間暗所に放置した後も作製直後と同様のＩＶ特性が得られたが、比較例１で作製した色素増感太陽電池Ｈ１Ｄは、実施例１で行った沸騰水処理を行わなかったため、一ヶ月暗所に放置した後、アルミニウム薄板の腐食が起こり、有効な変換効率が得られなかった。
よって、実施例１に示した本発明の色素増感太陽電池は優れた耐久性を有することが確認できた。
【００６１】
（比較例２）
図１０は従来の色素増感太陽電池の対極（絶縁層と白金膜）のパターン図である。図１０に示すように、対極用透明導電膜つきガラス基板２６をレーザースクライブにより、透明導電幕の一部を除去した（スクライブ部：１８）。その後、スパッターを用い、１．６ｃｍ×３ｃｍのパターンを持つ、白金膜（導電層）２５（膜厚：１０ｎｍ）を形成し、５００℃１時間焼成を行った。それを試料Ｈ２Ａとした。
従来の絶縁層と白金膜のパターン図である図１０に示すｉの長さは０．１ｃｍ、ｊの長さは０．５ｃｍ、ｋの長さは０．３ｃｍであった。
【００６２】
対極以外の作製方法は、実施例２に準じて作製を行った。
得られた色素増感太陽電池モジュールＨ２Ｄ（図示せず）に、ソーラーシミュレーター（ワコム社製）を用いて、強度：１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、開放電圧：３．０Ｖ、電流密度：１３ｍＡ／ｃｍ^２、ＦＦ：０．４５であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、電流密度：１２．６ｍＡ／ｃｍ^２、開放電圧：３．１Ｖ、ＦＦ：０．４８であった。
【００６３】
実施例２で作製した色素増感太陽電池モジュールと比較例２で作製した色素増感太陽電池モジュールは共に、一ヶ月間暗所に放置した後も作製直後と同様のＩＶ特性が得られた。
よって、実施例２で示した本発明の色素増感太陽電池モジュールは電子輸送層として透明導電膜を用いなくても、同等のＩＶ特性を得ることができるため、低コストで作製できることが確認できた。
【００６４】
（比較例３）
Ｐｔを堆積させたアルミニウム薄板に沸騰水処理を行わないこと以外は、実施例２に準じて作製を行った。
得られた色素増感太陽電池モジュールＨ２Ｄにソーラーシミュレーター（ワコム社製）を用いて、強度１００ｍＷ／ｃｍ^２の光を照射して、ＩＶ測定をすると、電流密度：１３ｍＡ／ｃｍ^２、開放電圧：３．１Ｖ、ＦＦ：０．５８３であった。その後一ヶ月間暗所に放置して、同様にＩＶ測定を行うと、開放電圧：０Ｖあった。
【００６５】
実施例２では一ヶ月間暗所に放置した後も作製直後と同様のＩＶ特性が得られたが、比較例２で作製した色素増感太陽電池は、実施例２で行った沸騰水処理を行わなかったため、一ヶ月暗所に放置後放置した後、アルミニウム薄板の腐食が起こり、有効な変換効率が得られなかった。
よって、実施例２に示した本発明の色素増感太陽電池モジュールは優れた耐久性を有することが確認できた。
【００６６】
【発明の効果】
本発明の色素増感太陽電池は優れた耐久性があり、色素増感太陽電池モジュールは、高い電圧を有し、対極に透明導電膜を用いないため、低コストである。したがって、かかる色素増感太陽電池および色素増感太陽電池モジュールは極めて有効である。
【図面の簡単な説明】
【図１】本発明の色素増感太陽電池の構造を示す概略断面図である。
【図２】本発明の色素増感太陽電池モジュールの概略断面図である。
【図３】本発明の対極の腐食防止層の構造を示す概略断面図である。
【図４】本発明の実施例１の色素増感太陽電池の構造を示す概略断面図である。
【図５】本発明の実施例２の対極のパターン図２Ａである。
【図６】本発明の実施例２の酸化チタン膜のパターン図２Ｂである。
【図７】本発明の実施例２のガラス基板に酸化チタン膜を配設した試料の上に配設した封止材料、絶縁層のパターン図２Ｃである。
【図８】本発明の実施例２の色素増感太陽電池モジュール２Ｄの概略断面図である。
【図９】本発明の実施例３の色素増感太陽電池モジュール３Ｄの概略断面図である。
【図１０】従来の色素増感太陽電池の対極のパターン図である。
【図１１】従来の色素増感太陽電池モジュールの対極の概略断面図である。
【符号の説明】
１ 第一支持体
２ 集電電極
３ 光電変換層
４ キャリア輸送層
５、１６ 対極
６ 第二支持体
７ 導電層
８ 封止層
９ 電子輸送層
１０ 触媒層
１１ 腐食防止層
１２、１９０ ガラス基板
１３ アルミニウム薄板
１４ Ｐｔ膜
１５ 酸化アルミニウム膜
１７ 酸化チタン膜
１８ スクライブ部
１９ 透明導電膜付きガラス基板
１９１ 透明導電膜
２０ 熱融着フィルム
２１ 導電層
２２ 酸化還元性電解液
２３ 封止材
２４ 接着剤
２５ 白金膜（Ｐｔ）
２６ 対極用透明導電膜付きガラス基板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dye-sensitized solar cell characterized in that the counter electrode includes an electron transport layer for transporting electrons, a catalyst layer made of a catalyst material, and a corrosion prevention layer for preventing corrosion of the electron transport layer, and to which the dye-sensitized solar cell is connected. The present invention relates to a dye-sensitized solar cell module.
[0002]
[Prior art]
Solar cells that use sunlight as an energy source to replace fossil fuels have attracted attention and various studies have been conducted. Currently, solar cells that are in practical use mainly use polycrystalline or amorphous silicon, but such solar cells still have high economic costs and energy costs in the manufacturing process.
[0003]
On the other hand, as a new type of solar cell, a wet solar cell using photo-induced electron transfer of a metal complex has been proposed (for example, Japanese Patent Publication No. 5-504023 (Patent Document 1), Japanese Patent No. 2664194). (Patent Document 2), International Publication No. WO94 / 05025 pamphlet (Patent Document 3)).
These wet solar cells are composed of a porous semiconductor electrode, a counter electrode, and an electrolyte layer sandwiched between the electrodes. In this wet solar cell, a photosensitizing dye having an absorption spectrum in the visible light region is adsorbed on the surface of a porous semiconductor electrode that is a photoelectric conversion material.
[0004]
When the porous semiconductor electrode of such a solar cell is irradiated with light, electrons are generated on this electrode side, and the electrons move to the counter electrode through the transparent conductive film and through the external electric circuit.
The electrons that have moved to the counter electrode are carried by the redox material in the iodine-based electrolyte and return to the porous semiconductor electrode. Such a process is repeated to extract electric energy.
Generally, a transparent conductive film such as ITO or FTO or a metal is used for the electron transport layer of the counter electrode.
In order to obtain a large voltage from these solar cells, it is necessary to connect many solar cells in series. In order to do so, a process is required to connect an electrode (collecting electrode) that collects the generated electrons and a counter electrode that passes the electrons carried through the external circuit to the redox body in the electrolyte.
[0005]
On the other hand, International Publication No. WO 00/57441 (Patent Document 4) discloses a metal fine particle in which a transparent conductive film is formed on a substrate used as a counter electrode, and the current collecting electrode and counter electrode are approximately the same as the distance between them. A module structure for connection is disclosed.
[0006]
The counter electrode of the solar cell shown in the above prior art has a structure as shown in FIG. 11 in which the catalyst layer 10 is disposed on the electron transport layer 9. Since an iodine-based redox electrolyte is generally used as the electrolyte, the electron transport layer and the electrolyte are in contact with each other at portions A and B in the figure. When ITO or a base metal is used for the electron transport layer, corrosion due to an electrolyte occurs, which causes a serious problem in performance deterioration and durability. In addition, SnO has relatively anticorrosive properties against iodine. ₂ If it is used for the electron transport layer, the cost becomes high.
In the above prior art, since the transparent conductive film is used for the electron transport layer used for the counter electrode, the cost is high.
[0007]
[Patent Document 1]
Japanese National Patent Publication No. 5-504023
[Patent Document 2]
Japanese Patent No. 2664194
[Patent Document 3]
International Publication No. WO94 / 05025 Pamphlet
[Patent Document 4]
International Publication No. WO00 / 57441 Pamphlet
[0008]
[Problems to be solved by the invention]
Even if ITO or base metal is used for the electron transport layer, it is an object to provide a dye-sensitized solar cell that is less likely to be corroded by an electrolyte, has good performance retention and good durability, and is low in cost. To do.
[0009]
[Means for Solving the Problems]
Thus, according to the present invention, the dye is adsorbed to the collecting electrode and the porous semiconductor layer from the first support side between the first support and the second support, at least one of which is made of a light transmissive material. In the dye-sensitized solar cell in which the photoelectric conversion layer, the carrier transport layer, and the counter electrode are laminated in this order, the counter electrode is a catalyst comprising an electron transport layer, a corrosion prevention layer, and a catalyst material that transports electrons from the second support side. Provided is a dye-sensitized solar cell that is laminated in the order of layers.
Further, at least two or more of the above dye-sensitized solar cells are connected in series, and the connection is made via the conductive layer to the insulating layer of another solar cell adjacent to the end of the conductive electrode of one solar cell. A dye-sensitized solar cell module is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the dye-sensitized solar cell of the present invention, the dye is applied to the collecting electrode and the porous semiconductor layer from the first support side between the first support and the second support, at least one of which is made of a light transmissive material. In the dye-sensitized solar cell in which the adsorbed photoelectric conversion layer, the carrier transport layer, and the counter electrode are stacked in this order, the counter electrode includes, from the second support side, an electron transport layer that transports electrons, a corrosion prevention layer, and a catalyst material. The catalyst layers are stacked in this order.
[0011]
The dye-sensitized solar cell of this invention is demonstrated using drawing.
FIG. 1 is a schematic cross-sectional view showing the structure of the dye-sensitized solar cell of the present invention.
The dye-sensitized solar cell of the present invention includes a current collecting electrode 2 that collects electrons generated on one side of a first support 1, a photoelectric conversion layer 3 in which a dye is adsorbed on a porous semiconductor surface, a carrier transport layer 4, and a counter electrode 5. The configuration is done.
The sealing layer 8 is formed on the outer periphery of the photoelectric conversion layer 3. The counter electrode 5 includes an electron transport layer 9 disposed on the second support 6, a catalyst layer 10 disposed thereon, and a corrosion prevention layer 11 that prevents corrosion of the electron transport layer 9. The carrier transport layer 4 is formed so that the second support 6 having an injection port (not shown) is overlapped with the first support 1 and the inside of the sealing layer 8 is filled. When the carrier transport layer 4 is an electrolytic solution, the electrolytic solution is injected from the injection port (not shown) into a portion surrounded by the first support 1, the second support 6 and the sealing layer 8. Form.
[0012]
Or when making a carrier transport layer into a gel electrolyte, a gel electrolyte is formed on the photoelectric converting layer 3, and the counter electrode 5 and the 2nd support body 6 are formed on it. In addition, the dye-sensitized solar cell in which the light incidence from the 1st support body 1 side is possible is obtained by using a light-transmitting material for the 1st support body 1. FIG. By using this structure, a dye-sensitized solar cell that is resistant to corrosion can be obtained.
[0013]
FIG. 2 is a schematic cross-sectional view of a dye-sensitized solar cell module configured using the dye-sensitized solar cell. The dye-sensitized solar cell module of the present invention is obtained by connecting the single dye-sensitized solar cells of FIG. 1 in series.
In this dye-sensitized solar cell module, two or more dye-sensitized solar cells of the present invention are connected in series, and the connection is made to the insulating layer of another solar cell adjacent to the end of the conductive electrode of one solar cell. This is done through a conductive layer. The conductive layer 7 is formed between the adjacent photoelectric conversion layers 3 and is in contact with the counter electrode 5 and the collector electrode 2. The sealing layer 8 is formed on the outer periphery of the module.
By using this structure, it is possible to connect many single dye-sensitized solar cells in series, and to manufacture a solar cell module that can extract a large voltage at low cost.
[0014]
<About support and collecting electrode>
The first support and the second support in the dye-sensitized solar cell of the present invention are not particularly limited as long as they are materials that are generally used as a support for dye-sensitized solar cells. For example, glass, PET film Etc. can be used. At least one of the first support and the second support needs to be transparent.
[0015]
Although the current collection electrode in the dye-sensitized solar cell of this invention should just have electroconductivity and light injects into a photoelectric converting layer, a transparent conductive film is preferable from a viewpoint of the incident amount of light.
As a material of the transparent conductive film, ITO or SnO ₂ : F, etc., as long as it is generally used as a transparent conductive film.
As the formation method, electrodeposition, electroless plating, coating or vapor deposition can be used, and the material is not particularly limited as long as it is made of a material generally used for an electrode of a dye-sensitized solar cell.
Pt, Ru, Pd, and C are preferable from the viewpoint of the effect of promoting the oxidation-reduction reaction.
Pt is particularly preferable from the viewpoint of the effect of promoting the redox reaction. In order to improve the adhesion between the catalyst layer 10 and the electron transport layer 9, heat treatment may be performed.
[0016]
The counter electrode of the dye-sensitized solar cell of the present invention includes an electron transport layer, a corrosion prevention layer, and a catalyst layer. Therefore, the components of the counter electrode will be described in order below.
<About the electron transport layer>
The electron transport layer 9 used for the counter electrode 5 is not particularly limited as long as it is a conductor, but from the viewpoint of conductivity, a metal or an alloy containing one or more kinds of metals is preferable.
More preferred is a metal capable of forming a highly corrosion-resistant compound or an alloy containing one or more metals, and relatively easy to form a corrosion-resistant compound, tin, titanium, aluminum, indium, molybdenum, tungsten Is more preferable.
Among these, aluminum is particularly preferable because the film thickness control is relatively easy.
[0017]
In addition, the method for forming the electron transport layer 9 is not particularly limited, but a CVD method, a sputtering method, an electroless plating method, an electrodeposition method, a printing method, a thin plate of metal or an alloy is attached with an adhesive or a double-sided tape, Generally, any method for forming an electrode may be used.
Among these, since formation is easy, the method of sticking a metal or alloy thin plate with an adhesive is preferable.
[0018]
<About corrosion prevention layer>
When the corrosion prevention layer 11 used for the counter electrode 5 has a structure in which a uniform film is formed on the electron transport layer 9, the corrosion prevention layer 11 is not particularly limited as long as it is a material resistant to corrosion, but a high melting point such as Ta or the like. A material containing a conductive polymer such as metal or PEDOT or a base metal material can be considered. The base metal material oxide is preferably aluminum oxide. In the case of using an insulator such as an oxide, in order to reduce the resistance, the thinner the film thickness, the better. However, the film thickness is preferably 50 nm or less.
[0019]
The corrosion prevention layer may be the same material as the electron transport layer, and is more preferably an oxide.
The method for forming the oxide is not particularly limited as long as it is generally a method for forming an oxide, but there are anodic oxidation, plasma oxidation, thermal oxidation, high-pressure steam treatment, boiling water treatment, and the like. Two or more may be combined.
[0020]
FIG. 3 is a view showing the structure of the corrosion prevention layer 11 of the counter electrode 5. The structure of the corrosion prevention layer 11 used for the counter electrode 5 is shown in FIG. 3 in which a uniform film is formed on the electron transport layer 9 and where the electron transport layer 9 and the catalyst layer 10 are not in contact with each other. The higher the coverage of the corrosion prevention layer 11, the better, but it is not necessary to be 100%.
[0021]
In the case of using the above structure, the method for forming the corrosion prevention layer 11 is not particularly limited as long as the corrosion prevention layer 11 can be uniformly formed, but a CVD method, a sputtering method, an electroless plating method, an electrodeposition method. , Spin coating, screen printing, gravure printing, and the like.
Further, when an insulator such as an oxide is used for the corrosion prevention layer 11, as a method for bringing the catalyst layer 10 and the electron transport layer 9 into contact, a pressing method, an ion implantation method, a sputtering method, or the like may be used.
In order to reduce the resistance, the thickness of the corrosion prevention layer 11 is preferably thinner than that of the electron transport layer 9.
The corrosion prevention layer 11 may be formed on a part of the electron transport layer from the viewpoint of preventing the electron transport layer 9 from being corroded due to the electrolyte used for the carrier transport layer 4 flowing around. .
From the viewpoint of reducing the series resistance component, in the dye-sensitized solar cell module of FIG. 2, the absence of the corrosion prevention layer 11 in the entire contact portion between the conductive layer 7 and the electron transport layer 9 reduces the series resistance component. It is preferable from the viewpoint.
[0022]
In the dye-sensitized solar cell of the present invention, a photoelectric conversion layer in which a dye is adsorbed on a porous semiconductor layer is used. Therefore, a photoelectric conversion layer, a porous semiconductor layer, a dye, and a solvent thereof will be described below.
<About photoelectric conversion layer>
The photoelectric conversion layer 3 in the dye-sensitized solar cell module of the present invention is formed by adsorbing a dye (photosensitizing dye) to the porous semiconductor layer formed on the first support 1. Generally, it is not particularly limited as long as it is made of a material used for a photoelectric conversion layer of a dye-sensitized solar cell.
[0023]
<Constituent material of porous semiconductor layer>
Examples of the constituent material of the porous semiconductor layer include inorganic semiconductors and organic semiconductors. Examples of the inorganic semiconductor include titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, and cadmium sulfide. Among these, titanium oxide is particularly preferable from the viewpoint of stability and safety. .
Titanium oxide means anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, various titanium oxides such as metatitanic acid and orthotitanic acid, or titanium hydroxide and hydrous titanium oxide. These inorganic semiconductors can be used alone or in combination of two or more.
[0024]
<About the formation method of a porous semiconductor layer>
It does not specifically limit as a method of forming a porous semiconductor layer on an electrode layer, A well-known method is mentioned. In particular,
(1) A method of applying a suspension containing semiconductor particles on an electrode layer, drying and / or firing,
(2) CVD method or MOCVD method using a predetermined source gas,
(3) PVD method, vapor deposition method or sputtering method using solid raw materials,
(4) Sol-gel method
Etc.
Formation of the porous semiconductor layer is also possible by a combination of the above methods.
[0025]
In order to adsorb more dye, the porous semiconductor layer preferably has a large specific surface area and is in the form of a porous film. The specific surface area is, for example, 10 to 200 m. ² / G is preferable. The film thickness of the porous semiconductor layer is not particularly limited, but is preferably about 0.1 to 50 μm, particularly preferably 1 μm to 35 μm.
[0026]
The method (1) for forming the porous semiconductor layer will be specifically described.
A semiconductor particle as a material is added to a dispersant, a solvent and the like and dispersed to prepare a suspension, and the suspension is applied onto the electrode layer. Examples of the coating method include known methods such as a doctor blade method, a squeegee method, a spin coating method, and a screen printing method.
Then, a porous semiconductor layer is obtained by drying and baking a coating film. In drying / firing, it is necessary to appropriately set conditions such as temperature, time, and atmosphere depending on the type of support, electrode and semiconductor particles to be used. Firing can be performed, for example, in the range of about 50 to 800 ° C. for about 10 seconds to 12 hours in an air atmosphere or an inert gas atmosphere. This drying and baking can be performed once at a single temperature or twice or more at different temperatures.
[0027]
<About semiconductor particles>
As the semiconductor particles, commercially available single or compound semiconductor particles having an average particle diameter in the range of 1 to 2000 nm can be used. Examples of suitable solvents for suspending the semiconductor particles include alcohols such as isopropyl alcohol, mixed solvents such as isopropyl alcohol / toluene, and water.
[0028]
Examples of the source gas used in the method (2) for forming the porous semiconductor layer include a single gas containing elements constituting the semiconductor or a mixture of two or more kinds.
Examples of the raw material solid used in the method (3) for forming the porous semiconductor layer include a single solid containing elements constituting the semiconductor, a combination of a plurality of solids, or a solid of a compound.
[0029]
The dye adsorbed on the surface of the porous semiconductor layer functions as a spectral sensitizer for improving the photoelectric conversion efficiency of the dye-sensitized solar cell. In particular, when an inorganic semiconductor such as a metal oxide is used as the porous semiconductor layer, it is preferable to adsorb a dye in order to increase sensitivity to light.
[0030]
The carrier transport layer 4 in the dye-sensitized solar cell of the present invention is formed on the photoelectric conversion layer 3, and the carrier transport layer has a function of transporting electrons present on the surface of the counter electrode 5 to the dye. Therefore, the carrier transport layer and the dye will be described below.
[0031]
<About carrier transport layer>
The carrier transport layer 4 in the dye-sensitized solar cell of the present invention is formed on the photoelectric conversion layer 3 and has a function of transporting electrons present on the surface of the counter electrode 5 to the dye in order to rapidly reduce the oxidized form of the dye. Bear. The carrier transport layer 4 is composed of an electrolytic solution, a solid electrolyte, a gel electrolyte, a molten salt gel electrolyte, and the like.
When an electrolytic solution is used for the carrier transport layer 4, at least the electrolytic solution is preferably composed of an electrolyte and a solvent.
[0032]
<About electrolyte>
As electrolytes, LiI, NaI, KI, CsI, CaI ₂ And iodides such as iodine salts of quaternary ammonium compounds such as tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, and the like, and I ₂ In combination with LiBr, NaBr, KBr, CsBr, CaBr ₂ And bromides such as bromides of quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide, and ₂ A metal complex such as ferrocyanate-ferricyanate or ferrocene-ferricinium ion; a sulfur compound such as sodium polysulfide or alkylthiol-alkyl disulfide; a viologen dye, hydroquinone-quinone, or the like. Among these, dimethylpropylimidazole iodide (DMPII), LiI, pyridinium iodide, imidazolium iodide and I ₂ Is preferable in terms of improving the open circuit voltage. Two or more of the above electrolytes may be mixed and used.
[0033]
<Electrolyte solvent>
Examples of such solvents include carbonate compounds such as ethylene carbonate and propylene carbonate; heterocyclic compounds such as 3-methyl-2-oxazolidinone; ether compounds such as dioxane and diethyl ether; ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene Glycol dialkyl ether, polypropylene glycol dialkyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, and other ethers; methanol, ethanol, and other alcohols; ethylene glycol, propylene Glycol, polyethylene glycol, polypro Glycol, polyhydric alcohols such as glycerin; acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile; dimethyl sulfoxide, aprotic polar substances such as sulfolane, and water.
[0034]
The electrolyte concentration in the electrolytic solution is preferably about 0.1 to 5 mol / liter in order to increase the conductivity.
As the solid electrolyte, a mixture of an electrolyte and an ion conductive polymer compound can be used. Examples of the ion conductive polymer compound include polar polymer compounds such as polyethers, polyesters, polyamines, and polysulfides.
[0035]
As a gel electrolyte, what was produced using electrolyte and a gelatinizer can be used. As the gelling agent, a polymer gelling agent is preferably used. Examples thereof include polymer gelling agents such as crosslinked polyacrylic resin derivatives, crosslinked polyacrylonitrile derivatives, polyalkylene oxide derivatives, silicon resins, and polymers having a nitrogen-containing heterocyclic quaternary compound salt structure in the side chain.
[0036]
As the molten salt gel electrolyte, a gel electrolyte material obtained by adding a room temperature molten salt can be used. As room temperature type molten salts, nitrogen-containing heterocyclic quaternary ammonium salt compounds such as pyridinium salts and imidazolium salts are preferably used.
When forming a carrier transport layer using a solid electrolyte, a gel electrolyte, or a molten salt gel electrolyte, the photoelectric conversion efficiency deteriorates unless the polymer electrolyte is sufficiently injected into the porous semiconductor layer. It is preferable that a certain monomer solution is impregnated in the porous semiconductor layer and then polymerized. Examples of the polymerization method include photopolymerization and thermal polymerization.
[0037]
<About pigments>
The dye is a compound having an absorption spectrum in the visible light region and / or the infrared light region, and in order to firmly adsorb the dye to the porous semiconductor layer, a carboxyl group, an alkoxy group, a hydroxyl group in the dye molecule. Those having an interlock group such as 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 excited dye and the conductive band of the porous semiconductor.
[0038]
Examples of the dye include a ruthenium dye, an azo dye, a quinone dye, a quinone imine dye, a quinacridone dye, a squarylium dye, a cyanine dye, a merocyanine dye, a triphenylmethane dye, a xanthene dye, and a porphyrin dye. Examples thereof include dyes, phthalocyanine dyes, perylene dyes, indigo dyes, and naphthalocyanine dyes.
In the present invention, the dye is adsorbed after the porous semiconductor layer is formed. Examples of the method for adsorbing the dye on the porous semiconductor layer include a method of immersing the porous semiconductor layer in a solution containing the dye.
[0039]
<Dye solvent>
The solvent used in the above solution is not particularly limited as long as it dissolves the pigment, and examples thereof include organic solvents such as alcohol, toluene, acetonitrile, chloroform, and dimethylformamide.
The dye concentration in the solution can be appropriately set according to the kind of the dye and solvent to be used, the condition of the dye adsorption step, and the like, for example, 1 × 10 ^-5 Mole / liter or more is preferred, 4 × 10 ^-4 About mol / liter is particularly preferable in that an appropriate amount of dye is adsorbed.
[0040]
Conditions such as temperature, pressure, and immersion time in the above immersion process can be appropriately set. Further, the immersion may be performed once or a plurality of times, and it is preferable to perform drying after the immersion.
[0041]
At least two dye-sensitized solar cells are connected in series, and the connection is made via a conductive layer to the insulating layer of another solar cell adjacent to the end of the conductive electrode of one solar cell. In the solar cell module, a conductive layer may be provided.
[0042]
<About conductive layer>
The material used for the conductive layer 7 is not particularly limited as long as it is conductive and resistant to swelling and corrosion by an electrolytic solution. From the viewpoint of corrosion resistance, a high melting point metal such as Ta, a conductive polymer An organic material such as, or a mixture of fine particles of metal such as silver or titanium and the conductive polymer is preferable.
The dye-sensitized solar cell module needs to be shielded from external air and moisture, and is preferably sealed.
[0043]
<About sealing material>
As a sealing material in the dye-sensitized solar cell module of the present invention, an ionomer resin film in which molecules of an ethylene-methacrylic acid copolymer are crosslinked with metal ions, liquid EVA (ethylene vinyl acetate) or vinylidene fluoride copolymer Various materials can be used depending on purposes such as EVA on the coalesced and acrylic resin mixture film, weather resistance, electrical insulation, light collection efficiency, cell protection (impact resistance), and the like.
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these.
[0044]
(Example 1)
FIG. 4 is a schematic cross-sectional view of a part of the sample 1A of the solar cell. In this example, aluminum was used for the electron transport layer. The aluminum thin plate 13 was cut into 0.5 cm × 1 cm, and Pt was deposited on the aluminum thin plate 13 by sputtering to form a Pt film (not shown). This was fired at 500 ° C. for 1 hour using an electric furnace (Denken Co., Ltd., product name: KDF-ES72). FIG. 3 shows the structure of the counter electrode 16. Thereafter, boiling water treatment was performed on the aluminum thin plate 13 at 95 ° C. or more for 24 hours, and a thin aluminum oxide film was formed on the portion of the aluminum thin plate 13 where Pt was not deposited, thereby preparing the counter electrode 16 (FIG. 3 and FIG. 4).
The thin aluminum oxide film then serves as a corrosion protection layer. The obtained counter electrode 16 is adhered to the glass substrate 12 (Corning Co., Ltd., code number 7059) after thinly applying and drying the adhesive 24 on the surface of the counter electrode 16 on which Pt is not deposited. The glass substrate 12 to which the counter electrode 16 is bonded is referred to as a sample 1A.
[0045]
Glass substrate with transparent conductive film (not shown) (made by Nippon Sheet Glass Co., Ltd., trade name: SnO ₂ Glass with film, SnO ₂ A titanium oxide film (not shown) is formed with a thickness of 5 mm □ and a thickness of 20 μm on the film thickness (500 nm). A photosensitizing dye represented by the formula (I) (Ruthenium 535 manufactured by Solaronix) in ethanol (manufactured by Kishida Chemical Co., Ltd.) and a concentration of 4 × 10 ^-4 A photosensitizing dye solution was obtained by dissolution so as to have a mole / liter. The resulting photosensitizing dye solution was refluxed for 1 hour to adsorb the dye to the titanium oxide film. A film in which a dye is absorbed in a titanium oxide film becomes a photoelectric conversion layer (not shown). This is designated as Sample 1B (not shown).
[0046]

[0047]
In FIG. 4, two holes were made in a portion of the sample 1A not covered with the aluminum thin plate 13 on the glass substrate 12.
Sample 1A in which a heat-sealing film (Mitsui-Dupont Polychemical Co., Ltd., trade name Himiran 1652) is disposed around the titanium oxide film (not shown) of sample 1B, and the glass plate of sample 1B and the hole are opened. The glass plate was sandwiched between clips and heated at 100 ° C. for 30 minutes to bond a heat-sealing film (not shown). The outside was sealed with an epoxy sealing material.
[0048]
From one hole of the glass substrate 12 of the obtained sample, redox electrolyte (DMPII (dimethylpropylimidazole iodide): 0.6 mol / liter iI: 0.1 mol, I ₂ : 0.1 mol, TBP (tertiary butyl pyridine): 0.5 mol, solvent: acetonitrile) were injected, glass beads were put into the holes, and sealing was performed with the epoxy sealing material 8. This electrolytic solution became the carrier transport layer 4, and the dye-sensitized solar cell 1D shown in FIG. 1 was obtained.
[0049]
Using a solar simulator (manufactured by Wacom) for the dye-sensitized solar cell 1D of the present invention shown in FIG. 1, the strength is 100 mW / cm. ² When the IV measurement was performed by irradiating the light, the conversion efficiency was 6.2%. Thereafter, the sample was left in the dark for one month, and the IV measurement was performed in the same manner. As a result, the conversion efficiency was 6.2%.
[0050]
(Example 2)
FIG. 3 is a cross-sectional view when an aluminum thin plate is used as the electron transport layer of the counter electrode of the dye-sensitized solar cell of the present invention. The aluminum thin plate 13 is cut into 3 cm × 1.6 cm, and Pt is deposited on the aluminum thin plate 13 by sputtering to form a Pt film 14. This was subjected to boiling water treatment in accordance with Example 1 to produce a counter electrode 16 (see FIG. 3), and the obtained counter electrode 16 was formed on a glass substrate 12 (Corning Corporation code number 7059, shape 4 cm × 10.2 cm × 0). The adhesive 24 is thinly applied to the surface of the counter electrode 16 on which the Pt is not deposited, dried, and then bonded.
FIG. 5 is a pattern diagram 2A of the counter electrode of the dye-sensitized solar cell of the present invention. The length of a shown in FIG. 5 is 0.1 cm, the length of b is 0.5 cm, and the length of c is 0.4 cm. The glass substrate 12 to which the counter electrode 16 is bonded is referred to as a sample 2A.
[0051]
FIG. 6 is a pattern diagram 2B of the titanium oxide film of the dye-sensitized solar cell of the present invention. A titanium oxide film 17 was applied in a 1 cm × 3 cm pattern on a glass substrate 19 with a transparent conductive film from which a part of the transparent conductive film was previously removed by laser scribing as shown in FIG. The length d shown in FIG. 6 is 1 cm, and the length e is 0.8 cm. Using an electric furnace (Denken Co., Ltd., product name: KDF-ES72), firing was performed at 500 ° C. for 1 hour. The thickness of the titanium oxide film 14 after firing was 20 μm. This is designated as Sample 2B.
Dye adsorption is performed according to Example 1, and the obtained sample is designated as Sample 2C.
[0052]
FIG. 7 is a pattern diagram 2C of a sealing material and an insulating layer disposed on a sample in which a titanium oxide film is disposed on a glass substrate of the dye-sensitized solar cell of the present invention. As shown in FIG. 7, f is 0.2 cm and g is 0.4 cm, with a heat-sealing film 20 (trade name Himiran 1652, thickness 50 μm, width 0.2 cm, manufactured by Mitsui DuPont Polychemical Co., Ltd.). As shown in FIG. H is 0 for the conductive layer (mixed material having a weight ratio of silver fine particles 45 μm: titanium fine particles 0.5 μm: polymeric silicon matrix = 1: 10: 4) connecting the counter electrode 16 and the glass substrate 19 with a transparent conductive film. It arrange | positions between the titanium oxides 17 so that it may become 4 cm. In the figure, 18 indicates a scribe part.
[0053]
In the sample 2A, two holes were formed per section surrounded by the heat-sealing film 20 and the conductive layer 21 except for the counter electrode part. The sample 2A was placed so that the portion g of the sample 2C shown in FIG. 7 protruded to the outside of the heat-sealing film by about 4 mm. The glass plate of sample 2C and the glass plate of sample 2A having a hole were sandwiched between clips and heated at 100 ° C. for 30 minutes to bond the heat-sealing film 20 and the conductive layer 21 together. The outside was sealed with an epoxy sealing material 23.
[0054]
FIG. 8 is a schematic cross-sectional view of the dye-sensitized solar cell module 2D. From one hole of the glass substrate 12 of the obtained sample, redox electrolyte solution 22 (0.6 mol of DMPII / 0.1 mol of lithol iI, I ₂ 0.1 mol, TBP 0.5 mol, solvent: acetonitrile), glass beads are put in all holes, and sealing is performed with an epoxy sealing material, thereby producing a dye-sensitized solar cell module 2D. (See FIG. 8). In the figure, 190 denotes a glass substrate and 191 denotes a transparent conductive film.
[0055]
Using a solar simulator (manufactured by Wacom) for the dye-sensitized solar cell module 2D of the present invention shown in FIG. 8, the strength is 100 mW / cm. ² When the IV measurement was performed by irradiating the light, current density: 12.8 mA / cm ² The open circuit voltage was 3.1 V and the FF was 0.552. Thereafter, the sample was left in a dark place for one month, and when IV measurement was performed in the same manner, current density: 12.6 mA / cm ² The open circuit voltage was 3.2 V and the FF was 0.555.
[0056]
(Example 3)
FIG. 9 is a schematic cross-sectional view of the dye-sensitized solar cell module 3D of the present invention. The aluminum thin plate 13 is covered with a mask so that the platinum film 14 is not deposited on the 0.2 cm × 3 cm portion on one side of the long side of the aluminum thin plate 13, and then platinum is deposited by sputtering, and the aluminum thin plate 13 is electrically conductive. Except that the layer 21 was in direct contact with the layer 21 as shown in FIG. 8, the production was performed according to Example 2, and the resulting dye-sensitized solar cell module 3D was obtained.
[0057]
Using a solar simulator (manufactured by Wacom) to the obtained dye-sensitized solar cell module 3D, the strength is 100 mW / cm. ² When the IV measurement was performed by irradiating the light, current density: 13 mA / cm ² The open circuit voltage was 3.1 V and the FF was 0.602. Thereafter, the sample was left in a dark place for one month, and when IV measurement was performed in the same manner, current density: 12.7 mA / cm ² The open circuit voltage was 3.2 V and the FF was 0.603.
[0058]
The dye-sensitized solar cell module 3D produced in Example 3 is different from the dye-sensitized solar cell module 2D produced in Example 2 in that the contact portion between the counter electrode 16 and the conductive layer 21 is the aluminum thin plate 13 and the conductive layer. Since 21 is in direct contact, FF is high.
Therefore, it was confirmed that the dye-sensitized solar cell module 3D of the present invention shown in Example 3 has a high FF.
[0059]
(Comparative Example 1)
Fabrication was carried out according to Example 1 except that the boiling aluminum treatment was not performed on the thin aluminum plate on which Pt was deposited.
Using a solar simulator (manufactured by Wacom) on the obtained dye-sensitized solar cell module H1D, an intensity of 100 mW / cm ² When the IV measurement was performed by irradiating the light, the conversion efficiency was 5.7%. Thereafter, the sample was left in a dark place for one month, and when IV measurement was performed in the same manner, the conversion efficiency was 0V.
[0060]
In Example 1, the IV characteristics similar to those immediately after production were obtained even after being left in a dark place for one month. However, the dye-sensitized solar cell H1D produced in Comparative Example 1 was subjected to boiling water treatment performed in Example 1. Therefore, after being left in the dark for one month, the aluminum thin plate was corroded, and an effective conversion efficiency could not be obtained.
Therefore, it was confirmed that the dye-sensitized solar cell of the present invention shown in Example 1 has excellent durability.
[0061]
(Comparative Example 2)
FIG. 10 is a pattern diagram of a counter electrode (insulating layer and platinum film) of a conventional dye-sensitized solar cell. As shown in FIG. 10, a part of the transparent conductive curtain was removed from the glass substrate 26 with a transparent conductive film for a counter electrode by laser scribing (scribe part: 18). Thereafter, a platinum film (conductive layer) 25 (film thickness: 10 nm) having a pattern of 1.6 cm × 3 cm was formed by sputtering, and baked at 500 ° C. for 1 hour. This was designated as Sample H2A.
As shown in FIG. 10, which is a pattern diagram of a conventional insulating layer and platinum film, the length of i is 0.1 cm, the length of j is 0.5 cm, and the length of k is 0.3 cm.
[0062]
Manufacturing methods other than the counter electrode were performed in accordance with Example 2.
For the obtained dye-sensitized solar cell module H2D (not shown), using a solar simulator (manufactured by Wacom), strength: 100 mW / cm ² When the IV measurement was performed by irradiating the light, open voltage: 3.0 V, current density: 13 mA / cm ² FF: 0.45. Thereafter, the sample was left in a dark place for one month, and when IV measurement was performed in the same manner, current density: 12.6 mA / cm ² The open circuit voltage was 3.1 V and the FF was 0.48.
[0063]
Both the dye-sensitized solar cell module produced in Example 2 and the dye-sensitized solar cell module produced in Comparative Example 2 exhibited IV characteristics similar to those immediately after production even after being left in a dark place for one month.
Therefore, it can be confirmed that the dye-sensitized solar cell module of the present invention shown in Example 2 can be produced at low cost because it can obtain the same IV characteristics without using a transparent conductive film as the electron transport layer. It was.
[0064]
(Comparative Example 3)
Fabrication was performed according to Example 2 except that the boiling water treatment was not performed on the thin aluminum plate on which Pt was deposited.
Using a solar simulator (manufactured by Wacom) on the obtained dye-sensitized solar cell module H2D, an intensity of 100 mW / cm ² When the IV measurement was performed by irradiating the light, current density: 13 mA / cm ² The open circuit voltage was 3.1 V and the FF was 0.583. Thereafter, the sample was left in a dark place for one month, and when IV measurement was performed in the same manner, the open circuit voltage was 0 V.
[0065]
In Example 2, the same IV characteristics as those immediately after the production were obtained even after being left in the dark for one month. However, the dye-sensitized solar cell produced in Comparative Example 2 was subjected to the boiling water treatment performed in Example 2. Since this was not performed, the aluminum thin plate was corroded after being left in the dark for one month, and effective conversion efficiency could not be obtained.
Therefore, it was confirmed that the dye-sensitized solar cell module of the present invention shown in Example 2 has excellent durability.
[0066]
【The invention's effect】
The dye-sensitized solar cell of the present invention has excellent durability, and the dye-sensitized solar cell module has a high voltage and does not use a transparent conductive film as a counter electrode, so that the cost is low. Therefore, the dye-sensitized solar cell and the dye-sensitized solar cell module are extremely effective.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the structure of a dye-sensitized solar cell of the present invention.
FIG. 2 is a schematic cross-sectional view of the dye-sensitized solar cell module of the present invention.
FIG. 3 is a schematic cross-sectional view showing the structure of the anticorrosion layer of the counter electrode of the present invention.
FIG. 4 is a schematic cross-sectional view showing the structure of the dye-sensitized solar cell of Example 1 of the present invention.
FIG. 5 is a pattern diagram 2A of a counter electrode according to Embodiment 2 of the present invention.
FIG. 6 is a pattern diagram 2B of a titanium oxide film according to Example 2 of the present invention.
FIG. 7 is a pattern diagram 2C of a sealing material and an insulating layer disposed on a sample in which a titanium oxide film is disposed on a glass substrate of Example 2 of the present invention.
FIG. 8 is a schematic cross-sectional view of a dye-sensitized solar cell module 2D according to Example 2 of the present invention.
FIG. 9 is a schematic cross-sectional view of a dye-sensitized solar cell module 3D according to Example 3 of the present invention.
FIG. 10 is a pattern diagram of a counter electrode of a conventional dye-sensitized solar cell.
FIG. 11 is a schematic cross-sectional view of a counter electrode of a conventional dye-sensitized solar cell module.
[Explanation of symbols]
1 First support
2 Current collecting electrode
3 Photoelectric conversion layer
4 Carrier transport layer
5, 16 Counter electrode
6 Second support
7 Conductive layer
8 Sealing layer
9 Electron transport layer
10 Catalyst layer
11 Corrosion prevention layer
12, 190 Glass substrate
13 Aluminum sheet
14 Pt film
15 Aluminum oxide film
17 Titanium oxide film
18 Scribe club
19 Glass substrate with transparent conductive film
191 Transparent conductive film
20 heat sealing film
21 Conductive layer
22 Redox electrolyte
23 Sealing material
24 Adhesive
25 Platinum membrane (Pt)
26 Glass substrate with transparent conductive film for counter electrode

Claims (10)

Between the first support and the second support, at least one of which is made of a light-transmitting material, from the first support side, the collector electrode, the photoelectric conversion layer in which the porous semiconductor layer is adsorbed, and the carrier transport layer In the dye-sensitized solar cell laminated in the order of the counter electrode, the counter electrode is laminated from the second support side in the order of an electron transport layer for transporting electrons, a corrosion prevention layer, and a catalyst layer made of a catalyst material. A dye-sensitized solar cell characterized by The dye-sensitized solar cell according to claim 1, wherein the electron transport layer is covered with a corrosion prevention layer. The dye-sensitized solar cell according to claim 1 or 2, wherein the corrosion prevention layer is composed of a layer containing an electron transport layer material. The dye-sensitized solar cell according to claim 3, wherein a thickness of the corrosion prevention layer is thinner than a thickness of the electron transport layer. The dye-sensitized solar cell according to claim 3 or 4, wherein the corrosion prevention layer comprises an oxide layer. The dye-sensitized solar cell according to any one of claims 1 to 5, wherein the electron transport layer is made of a metal. The dye-sensitized solar cell according to claim 6, wherein the metal is Al. Carrier transport layer, dimethylpropyl imidazole iodide (DMPII), LiI, according to any one of claims 1 to 7 as an electrolyte solution obtained by dispersing _{I 2} and tertiary butyl pyridine (TBP) in a solvent dye Sensitized solar cell. The dye-sensitized solar cell according to any one of claims 1 to 8, wherein at least two or more of the dye-sensitized solar cells are connected in series, and the connection of another solar cell adjacent to the end portion of the conductive electrode of one solar cell. A dye-sensitized solar cell module which is formed on an insulating layer via a conductive layer. The dye-sensitized solar cell module according to claim 9, wherein at least a part of a contact portion between the conductive layer and the counter electrode is in direct contact with the conductive layer and the electron transport layer.

Images