JP5680996B2 - Dye-sensitized solar cell module and manufacturing method thereof - Google Patents

Dye-sensitized solar cell module and manufacturing method thereof Download PDF

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JP5680996B2
JP5680996B2 JP2011044677A JP2011044677A JP5680996B2 JP 5680996 B2 JP5680996 B2 JP 5680996B2 JP 2011044677 A JP2011044677 A JP 2011044677A JP 2011044677 A JP2011044677 A JP 2011044677A JP 5680996 B2 JP5680996 B2 JP 5680996B2
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sensitized solar
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JP2012182041A (en
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芳泰 磯部
芳泰 磯部
和寛 山本
和寛 山本
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Fujikura Ltd
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Priority to PCT/JP2012/054861 priority patent/WO2012118050A1/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells

Description

本発明は、色素増感太陽電池モジュール及びその製造方法に関する。   The present invention relates to a dye-sensitized solar cell module and a method for manufacturing the same.

光電変換素子モジュールとして、安価で、高い光電変換効率が得られることから色素増感太陽電池モジュールが注目されており、色素増感太陽電池モジュールに関して種々の開発が行われている。   As a photoelectric conversion element module, a dye-sensitized solar cell module has attracted attention because it is inexpensive and has high photoelectric conversion efficiency, and various developments have been made on the dye-sensitized solar cell module.

色素増感太陽電池モジュールは一般に、複数個の直列に接続された色素増感太陽電池を備えており、各色素増感太陽電池は、作用極と、対極と、作用極と対極とを連結する封止部とを備えている。そして、作用極は、透明基板と、その上に形成された透明導電膜と、透明導電膜の上に設けられる酸化物半導体層とを有している。このような色素増感太陽電池モジュールとして、例えば下記特許文献１記載のものが知られている。下記特許文献１には、隣り合う２つの色素増感太陽電池において、一方の色素増感太陽電池の対極の縁部と、他方の色素増感太陽電池の透明導電膜とが、隣り合う封止部の間で、はんだ又は導電性ペーストなどの導電部材を介して接続された色素増感太陽電池モジュールが開示されている。   A dye-sensitized solar cell module generally includes a plurality of dye-sensitized solar cells connected in series, and each dye-sensitized solar cell connects a working electrode, a counter electrode, and a working electrode and a counter electrode. And a sealing portion. The working electrode includes a transparent substrate, a transparent conductive film formed thereon, and an oxide semiconductor layer provided on the transparent conductive film. As such a dye-sensitized solar cell module, the thing of the following patent document 1 is known, for example. In Patent Document 1 below, in two adjacent dye-sensitized solar cells, the edge of the counter electrode of one dye-sensitized solar cell and the transparent conductive film of the other dye-sensitized solar cell are adjacently sealed. There is disclosed a dye-sensitized solar cell module connected between parts via a conductive member such as solder or conductive paste.

国際公開第2009/144949号公報International Publication No. 2009/144949

ところで、色素増感太陽電池においては、裏面より直接電気を取り出すことができるため、対極に金属を用いることが好ましい。しかし、金属の中には、電解質に含有されるヨウ素等に対して耐腐食性を有しないものも存在する。このため、色素増感太陽電池においては、対極の金属として、耐食性の高い不動態膜を有する金属を用いる必要がある。   By the way, in a dye-sensitized solar cell, since electricity can be taken out directly from the back surface, it is preferable to use a metal for the counter electrode. However, some metals do not have corrosion resistance against iodine or the like contained in the electrolyte. For this reason, in a dye-sensitized solar cell, it is necessary to use the metal which has a passive film with high corrosion resistance as a metal of a counter electrode.

しかし、対極の金属として、耐食性の高い不動態膜を有する金属を用いる場合、上記特許文献１に記載の色素増感太陽電池モジュールの製造方法は、以下に示す課題を有していた。   However, when a metal having a passive film having high corrosion resistance is used as the counter electrode metal, the method for producing a dye-sensitized solar cell module described in Patent Document 1 has the following problems.

すなわち、対極の金属として、耐食性の高い不動態膜を有する金属を用いる場合、はんだや導電性ペーストと対極とを接続させようとしても、対極の不動態膜によりはんだや導電性ペーストが対極と接着しないか、接着しても接触抵抗が高く、接続信頼性や導電性が十分でない。また金属には、不動態とまではいかなくても、必ず表面に薄い酸化膜が形成されるため、不動態膜を形成しない金属を用いても、接触抵抗が高く、接着力も十分ではない。   In other words, when a metal having a passive film with high corrosion resistance is used as the counter electrode metal, the solder or conductive paste is bonded to the counter electrode by the counter electrode passive film, even if the solder or conductive paste is connected to the counter electrode. No contact resistance is high even when bonded, and connection reliability and conductivity are not sufficient. Even if the metal is not passive, a thin oxide film is always formed on the surface. Therefore, even when a metal that does not form a passive film is used, the contact resistance is high and the adhesive strength is not sufficient.

また、はんだや導電性ペーストを用いる場合、熱を加えて溶融させ、接着させなければならないため、加熱温度によっては、多孔質酸化物半導体層に担持された光増感色素が劣化するおそれがある。   In addition, when solder or conductive paste is used, heat must be applied to melt and bond, so depending on the heating temperature, the photosensitizing dye carried on the porous oxide semiconductor layer may deteriorate. .

従って、優れた導電性及び接続信頼性を有し、光増感色素の劣化が十分に抑制された色素増感太陽電池モジュールの製造方法が求められていた。   Therefore, there has been a demand for a method for producing a dye-sensitized solar cell module that has excellent conductivity and connection reliability and in which deterioration of the photosensitizing dye is sufficiently suppressed.

本発明は上記事項に鑑みてなされたものであり、優れた導電性及び接続信頼性を有し、光増感色素の劣化が十分に抑制された色素増感太陽電池モジュールを製造できる色素増感太陽電池モジュールの製造方法及び色素増感太陽電池モジュールを提供することを目的とする。   The present invention has been made in view of the above-described matters, and has dye-sensitized solar cell modules capable of producing a dye-sensitized solar cell module that has excellent conductivity and connection reliability and in which deterioration of the photosensitizing dye is sufficiently suppressed. It aims at providing the manufacturing method of a solar cell module, and a dye-sensitized solar cell module.

本発明者らは上記課題を解決するため鋭意研究を重ねた結果、以下の発明により、上記課題を解決し得ることを見出し、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following invention, and have completed the present invention.

すなわち本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と、前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを有し、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、前記接続工程において、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とを抵抗溶接により直接接続し、前記接続工程において、前記抵抗溶接を、前記集電配線の上に前記第２電極を接触させた状態で、２つの抵抗溶接用の電極を、前記第２電極の表面に当接させることによって行う色素増感太陽電池モジュールの製造方法である。
That is, the present invention provides a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically. Are connected in series and electrically to manufacture the dye-sensitized solar cell module unit, and the dye-sensitized solar cell includes a transparent substrate and a transparent conductive film provided on the transparent substrate. An electrode; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; the oxide semiconductor layer provided on the first electrode or the second electrode; and the transparent conductive film A current collector wiring provided on the first electrode; an electrolyte provided between the first electrode and the second electrode; and a sealing portion for connecting the first electrode and the second electrode; Pigment One of the transparent substrate as the transparent substrate in the sensitive solar cells commonly used, in the connecting step, the metal of the second electrode of one of the dye-sensitized solar cell of the two dye-sensitized solar cell adjacent the substrate And the current collector wiring in the first electrode of the other dye-sensitized solar cell are directly connected by resistance welding, and in the connecting step, the resistance welding is performed by placing the second electrode on the current collector wiring. This is a method for producing a dye-sensitized solar cell module , in which two resistance welding electrodes are brought into contact with the surface of the second electrode while being in contact with each other.

この製造方法によれば、接続工程において、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極と、他方の色素増感太陽電池の前記第１電極における前記集電配線とが抵抗溶接により接続される。ここで、抵抗溶接は、２本の電極を第２電極及び集電配線又はそのいずれか一方に押し当てて、両者間に電流を流すことにより、第２電極と集電配線との接触部分で熱を発生させ、この熱により第２電極と集電配線の両方を溶融させて両者を接続させる方法である。このとき、熱は金属基板と集電配線との接触部分にしか発生しない。また、抵抗溶接においては通常、電流を流す時間は短時間（数ミリ秒）であるため、熱が発生する時間も短い。このため、熱が加えられる場所を局所領域に抑えることができる。従って、封止工程の後、第２電極を集電配線に接続する場合でも、酸化物半導体層に担持された光増感色素の劣化を十分に抑制することができる。   According to this manufacturing method, in the connecting step, the second electrode of one dye-sensitized solar cell among the two adjacent dye-sensitized solar cells and the first electrode of the other dye-sensitized solar cell. The current collector wiring is connected by resistance welding. Here, resistance welding is performed at the contact portion between the second electrode and the current collector wiring by pressing the two electrodes against the second electrode and / or the current collector wiring and causing a current to flow between them. In this method, heat is generated, both the second electrode and the current collector wiring are melted by this heat, and both are connected. At this time, heat is generated only at the contact portion between the metal substrate and the current collector wiring. In resistance welding, the current is usually supplied for a short time (several milliseconds), so the time for generating heat is also short. For this reason, the place where heat is applied can be suppressed to a local region. Therefore, even when the second electrode is connected to the current collector wiring after the sealing step, deterioration of the photosensitizing dye carried on the oxide semiconductor layer can be sufficiently suppressed.

さらに接続工程により、第２電極と集電配線とを溶融させて接合させるため、両者の間に合金部が形成される。このため、金属基板と集電配線との接合強度が大きくなり、得られた複数の色素増感太陽電池を直列に接続した場合に、優れた接続信頼性を有する色素増感太陽電池モジュールを得ることができる。また第２電極と集電配線との間に合金部が設けられることで、第２電極と集電配線との間の接触抵抗も低下させることができる。従って、得られる色素増感太陽電池モジュールは、優れた導電性も有することとなる。   Further, in the connecting step, the second electrode and the current collector wiring are melted and joined, so that an alloy part is formed between them. For this reason, the bonding strength between the metal substrate and the current collector wiring is increased, and when a plurality of the obtained dye-sensitized solar cells are connected in series, a dye-sensitized solar cell module having excellent connection reliability is obtained. be able to. Moreover, the contact resistance between a 2nd electrode and current collection wiring can also be reduced by providing an alloy part between 2nd electrode and current collection wiring. Therefore, the obtained dye-sensitized solar cell module also has excellent conductivity.

また、第２電極と集電配線とを抵抗溶接により接続する際に、２つの抵抗溶接用電極を集電配線及び第２電極の金属基板のうち第１電極側の表面に押し当てずに済む。このため、第２電極の金属基板のうち第１電極側の表面に、抵抗溶接用電極の溶着による不純物を介在させないという利点が得られる。また、集電配線に抵抗溶接用電極を押し当てずに済むので、省スペースにおいて、溶接することが出来る。
 Further , when connecting the second electrode and the current collector wiring by resistance welding, it is not necessary to press the two resistance welding electrodes against the surface on the first electrode side of the current collector wiring and the metal substrate of the second electrode. . For this reason, the advantage that the impurity by welding of the electrode for resistance welding does not interpose on the surface by the side of the 1st electrode among the metal substrates of the 2nd electrode is acquired. In addition, since it is not necessary to press the resistance welding electrode against the current collector wiring, welding can be performed in a small space.

前記接続工程において、前記抵抗溶接を3〜20ミリ秒行うことが好ましい。   In the connecting step, the resistance welding is preferably performed for 3 to 20 milliseconds.

この場合、第２電極と集電配線との接続強度をより十分に向上させることができると共に、合金部の厚さが適度になり、集電配線と金属基板との間の抵抗をより十分に低くすることができる。   In this case, the connection strength between the second electrode and the current collector wiring can be improved more sufficiently, the thickness of the alloy portion becomes appropriate, and the resistance between the current collector wiring and the metal substrate can be more sufficiently improved. Can be lowered.

前記第２電極の厚さは9〜200μｍであることが好ましい。第２電極の厚さが9μｍ以上であると、9μｍ未満である場合に比べて第２電極の強度がより大きいため、抵抗溶接に際して変形しにくくなる。一方、第２電極の厚さが、200μｍ以下であると、200μｍを超える場合に比べてより短時間で第２電極と集電配線とを接続できる。また第２電極に可撓性を持たせることもできる。   The thickness of the second electrode is preferably 9 to 200 μm. If the thickness of the second electrode is 9 μm or more, the strength of the second electrode is greater than when the thickness is less than 9 μm. On the other hand, when the thickness of the second electrode is 200 μm or less, the second electrode and the current collector wiring can be connected in a shorter time than when the thickness exceeds 200 μm. Further, the second electrode can be flexible.

前記集電配線の厚さは0.1〜50μｍであることが好ましい。   The thickness of the current collecting wiring is preferably 0.1 to 50 μm.

この場合、集電配線の厚さが0.1μｍ以上であると、0.1μｍ未満である場合に比べて強度がより大きいため、抵抗溶接に際して変形しにくくなる。一方、集電配線の厚さが、50μｍ以下であると、50μｍを超える場合に比べてより短時間で第２電極と集電配線とを接続できる。   In this case, when the thickness of the current collecting wiring is 0.1 μm or more, the strength is higher than that when the current collecting wiring is less than 0.1 μm. On the other hand, when the thickness of the current collecting wiring is 50 μm or less, the second electrode and the current collecting wiring can be connected in a shorter time than when the thickness exceeds 50 μm.

また本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と、前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを有し、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、前記接続工程が、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板を、他方の色素増感太陽電池の前記第１電極における前記集電配線に接合されたインサート材と抵抗溶接により接続する工程を含み、前記インサート材が前記金属基板及び前記集電配線よりも低い抵抗を有する色素増感太陽電池モジュールの製造方法である。
The present invention also provides a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically. Are connected in series and electrically to manufacture the dye-sensitized solar cell module unit, and the dye-sensitized solar cell includes a transparent substrate and a transparent conductive film provided on the transparent substrate. An electrode; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; the oxide semiconductor layer provided on the first electrode or the second electrode; and the transparent conductive film A current collector wiring provided on the first electrode; an electrolyte provided between the first electrode and the second electrode; and a sealing portion for connecting the first electrode and the second electrode; Dye sensitization The transparent substrate one transparent substrate is commonly used as the solar cell, wherein the connecting step is, the metal substrate of the second electrode of one of the dye-sensitized solar cell of the two dye-sensitized solar cell adjacent to And a step of connecting by resistance welding to an insert material joined to the current collector wiring in the first electrode of the other dye-sensitized solar cell , wherein the insert material has a lower resistance than the metal substrate and the current collector wiring it is a manufacturing method of a dye-sensitized solar cell module to have a.

また本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを有し、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、前記第２電極が、前記金属基板に対して前記第１電極と反対側に、前記金属基板よりも低い抵抗を有する導電材をさらに有し、前記接続工程において、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記導電材と、他方の色素増感太陽電池の前記第１電極における前記集電配線とを抵抗溶接により接続する色素増感太陽電池モジュールの製造方法である。 The present invention also provides a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically. Are connected in series and electrically to manufacture the dye-sensitized solar cell module unit, and the dye-sensitized solar cell includes a transparent substrate and a transparent conductive film provided on the transparent substrate. An electrode; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; the oxide semiconductor layer provided on the first electrode or the second electrode; and the transparent conductive film A plurality of dyes, comprising: a current collector wiring provided on the top; an electrolyte provided between the first electrode and the second electrode; and a sealing portion for connecting the first electrode and the second electrode. Sensitization The transparent substrate one transparent substrate is commonly used as the battery, the second electrode, the opposite to the first electrode to the metal substrate, further a conductive material having a lower resistance than the metal substrate And in the connecting step , in the conductive material of the second electrode of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells, and the first electrode of the other dye-sensitized solar cell. It is a manufacturing method of the dye-sensitized solar cell module which connects the said current collection wiring by resistance welding.

また本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と、前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを備え、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とが直接接続され、前記集電配線と前記第２電極の金属基板との間に、前記金属基板の金属と前記集電配線の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュールである。   The present invention also provides a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically, wherein the dye-sensitized solar cell includes a transparent substrate and A first electrode having a transparent conductive film provided on the transparent substrate; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; and the first electrode or the second electrode. An oxide semiconductor layer provided on the electrode, a current collector wiring provided on the transparent conductive film, an electrolyte provided between the first electrode and the second electrode, the first electrode, and the second electrode And one transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells, and one of the two adjacent dye-sensitized solar cells is dye-sensitized solar. Battery The metal substrate of the second electrode and the current collector wiring in the first electrode of the other dye-sensitized solar cell are directly connected, and between the current collector wiring and the metal substrate of the second electrode, It is a dye-sensitized solar cell module provided with an alloy part made of an alloy of the metal of the metal substrate and the metal of the current collector wiring.

この発明によれば、第２電極の金属基板と集電配線との間に、第２電極における金属基板の金属と、集電配線の金属との合金からなる合金部が設けられているため、第２電極と集電配線との接続強度が大きくなり、優れた接続信頼性が得られる。また第２電極の金属基板と集電配線との間に合金部が設けられることで、第２電極の金属基板と集電配線との間の接触抵抗も低下させることができる。   According to this invention, an alloy portion made of an alloy of the metal of the metal substrate of the second electrode and the metal of the current collector wiring is provided between the metal substrate of the second electrode and the current collector wiring. The connection strength between the second electrode and the current collector wiring is increased, and excellent connection reliability is obtained. Further, by providing the alloy portion between the metal substrate of the second electrode and the current collector wiring, the contact resistance between the metal substrate of the second electrode and the current collector wiring can also be reduced.

また本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と、前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを備え、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とがインサート材を介して接続され、前記金属基板と前記インサート材との間に、前記金属基板の金属と前記インサート材の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュールであってもよい。   The present invention also provides a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically, wherein the dye-sensitized solar cell includes a transparent substrate and A first electrode having a transparent conductive film provided on the transparent substrate; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; and the first electrode or the second electrode. An oxide semiconductor layer provided on the electrode, a current collector wiring provided on the transparent conductive film, an electrolyte provided between the first electrode and the second electrode, the first electrode, and the second electrode And one transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells, and one of the two adjacent dye-sensitized solar cells is dye-sensitized solar. Battery The metal substrate of the second electrode and the current collector wiring in the first electrode of the other dye-sensitized solar cell are connected via an insert material, and the metal substrate and the insert material, It may be a dye-sensitized solar cell module in which an alloy part made of an alloy of a metal of a metal substrate and a metal of the insert material is provided.

この発明によれば、第２電極の金属基板と集電配線に接続したインサート材との間に、第２電極における金属基板の金属と、インサート材の金属との合金からなる合金部が設けられているため、第２電極の金属基板とインサート材との接続強度が大きくなり、優れた接続信頼性が得られる。また第２電極の金属基板とインサート材との間に合金部が設けられることで、第２電極の金属基板とインサート材との間の接触抵抗も低下させることができる。   According to this invention, an alloy part made of an alloy of the metal of the metal substrate and the metal of the insert material in the second electrode is provided between the metal substrate of the second electrode and the insert material connected to the current collector wiring. Therefore, the connection strength between the metal substrate of the second electrode and the insert material is increased, and excellent connection reliability is obtained. Moreover, the contact resistance between the metal substrate of the second electrode and the insert material can be reduced by providing the alloy part between the metal substrate of the second electrode and the insert material.

さらに本発明は、直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、前記色素増感太陽電池が、透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、前記第１電極又は前記第２電極に設けられる酸化物半導体層と、前記透明導電膜上に設けられる集電配線と、前記第１電極と前記第２電極との間に設けられる電解質と、前記第１電極及び前記第２電極を連結させる封止部とを備え、前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、前記第２電極が、前記金属基板に対して前記第１電極と反対側に、前記金属基板よりも低い抵抗を有する導電材をさらに有し、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記導電材と、他方の色素増感太陽電池の前記第１電極における前記集電配線とが直接接続され、前記集電配線と前記導電材との間に、前記集電配線の金属と前記導電材の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュールであってもよい。   Furthermore, the present invention provides a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically, wherein the dye-sensitized solar cell includes a transparent substrate and A first electrode having a transparent conductive film provided on the transparent substrate; a second electrode including a metal substrate made of a metal having a passive film facing the first electrode; and the first electrode or the second electrode. An oxide semiconductor layer provided on the electrode, a current collector wiring provided on the transparent conductive film, an electrolyte provided between the first electrode and the second electrode, the first electrode, and the second electrode And a transparent part is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells, and the second electrode is connected to the metal substrate with the first electrode. On the other side The conductive material of the second electrode of one dye-sensitized solar cell of the two adjacent dye-sensitized solar cells, and the other dye-sensitized, further comprising a conductive material having a lower resistance than the metal substrate. The current collector wiring in the first electrode of the solar cell is directly connected, and an alloy portion made of an alloy of the metal of the current collector wiring and the metal of the conductive material between the current collector wiring and the conductive material. The dye-sensitized solar cell module may be provided.

この発明によれば、第２電極の導電材と、集電配線との間に、第２電極における導電材の金属と、集電配線の金属との合金からなる合金部が設けられているため、第２電極と集電配線との接続強度が大きくなり、優れた接続信頼性が得られる。また第２電極の導電材と集電配線との間に合金部が設けられることで、第２電極と集電配線との間の接触抵抗も低下させることができる。   According to the present invention, an alloy portion made of an alloy of the metal of the conductive material in the second electrode and the metal of the current collector wiring is provided between the conductive material of the second electrode and the current collector wiring. The connection strength between the second electrode and the current collector wiring is increased, and excellent connection reliability is obtained. Moreover, the contact resistance between a 2nd electrode and current collection wiring can also be reduced by providing an alloy part between the electrically-conductive material of 2nd electrode, and current collection wiring.

本発明によれば、優れた導電性及び接続信頼性を有し、光増感色素の劣化が十分に抑制された色素増感太陽電池モジュールを製造できる色素増感太陽電池モジュールの製造方法及び色素増感太陽電池モジュールが提供される。   ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a dye-sensitized solar cell module which can manufacture the dye-sensitized solar cell module which has the outstanding electroconductivity and connection reliability, and the deterioration of the photosensitizing dye was fully suppressed, and a pigment | dye A sensitized solar cell module is provided.

本発明の色素増感太陽電池モジュールの一実施形態を示す平面図である。It is a top view which shows one Embodiment of the dye-sensitized solar cell module of this invention. 図１の一部切欠き部分拡大図である。FIG. 2 is a partially cutaway enlarged view of FIG. 1. 図２のＩＩＩ−ＩＩＩ線に沿った断面図である。It is sectional drawing along the III-III line of FIG. 図１の第１電極を示す平面図である。It is a top view which shows the 1st electrode of FIG. 抵抗溶接によりランド部及び突出部が接続されていることを示す図である。It is a figure which shows that the land part and the protrusion part are connected by resistance welding. 突出部とランド部との間に合金部が形成されていることを示す図である。It is a figure which shows that the alloy part is formed between the protrusion part and the land part. 本発明の色素増感太陽電池モジュールの他の実施形態を示す一部切欠き部分平面図である。It is a partially notched partial top view which shows other embodiment of the dye-sensitized solar cell module of this invention. 図７の色素増感太陽電池モジュールのＶＩＩＩ−ＶＩＩＩ線に沿った断面図である。It is sectional drawing along the VIII-VIII line of the dye-sensitized solar cell module of FIG. 本発明の色素増感太陽電池モジュールのさらに他の実施形態を示す部分断面図である。It is a fragmentary sectional view which shows other embodiment of the dye-sensitized solar cell module of this invention.

以下、本発明の実施形態について詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail.

＜第１実施形態＞
まず本発明の色素増感太陽電池モジュールの第１実施形態について説明する。図１は、本発明の色素増感太陽電池モジュールの第１実施形態を示す底面図である。 <First Embodiment>
First, a first embodiment of the dye-sensitized solar cell module of the present invention will be described. FIG. 1 is a bottom view showing a first embodiment of the dye-sensitized solar cell module of the present invention.

図１に示すように、色素増感太陽電池モジュール２００は、２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂを有している。色素増感太陽電池モジュールユニット１００Ａ，１００Ｂは直列且つ電気的に接続されている。色素増感太陽電池モジュールユニット１００Ａ，１００Ｂは、複数の色素増感太陽電池５０を有し、複数の色素増感太陽電池５０は直列且つ電気的に接続されている。ここで、２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂは、２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂの各々における色素増感太陽電池５０の配列方向が互いに平行となるように配列されている。以下、説明の便宜上、色素増感太陽電池モジュールユニット１００Ａにおける４つの色素増感太陽電池５０を色素増感太陽電池５０Ａ〜５０Ｄと、色素増感太陽電池モジュールユニット１００Ｂにおける４つの色素増感太陽電池５０を色素増感太陽電池５０Ｅ〜５０Ｈと呼ぶことがある。   As shown in FIG. 1, the dye-sensitized solar cell module 200 has two dye-sensitized solar cell module units 100A and 100B. The dye-sensitized solar cell module units 100A and 100B are connected in series and electrically. The dye-sensitized solar cell module units 100A and 100B have a plurality of dye-sensitized solar cells 50, and the plurality of dye-sensitized solar cells 50 are connected in series and electrically. Here, the two dye-sensitized solar cell module units 100A and 100B are arranged so that the arrangement directions of the dye-sensitized solar cells 50 in each of the two dye-sensitized solar cell module units 100A and 100B are parallel to each other. ing. Hereinafter, for convenience of explanation, the four dye-sensitized solar cells 50 in the dye-sensitized solar cell module unit 100A are referred to as the dye-sensitized solar cells 50A to 50D and the four dye-sensitized solar cells in the dye-sensitized solar cell module unit 100B. 50 may be referred to as dye-sensitized solar cells 50E to 50H.

図２は、図１の一部切欠き部分拡大図、図３は、図２のＩＩＩ−ＩＩＩ線に沿った断面図、図４は、図３の作用極を示す平面図である。図３に示すように、複数の色素増感太陽電池５０の各々は、作用極１０と、作用極１０に対向する対極２０と、作用極１０及び対極２０を連結させる封止部３０とを備えており、作用極１０、対極２０及び封止部３０によって形成されるセル空間には電解質４０が充填されている。   2 is a partially cutaway enlarged view of FIG. 1, FIG. 3 is a sectional view taken along line III-III of FIG. 2, and FIG. 4 is a plan view showing the working electrode of FIG. As shown in FIG. 3, each of the plurality of dye-sensitized solar cells 50 includes a working electrode 10, a counter electrode 20 that faces the working electrode 10, and a sealing unit 30 that connects the working electrode 10 and the counter electrode 20. The cell space formed by the working electrode 10, the counter electrode 20, and the sealing portion 30 is filled with an electrolyte 40.

次に、隣り合う色素増感太陽電池５０間の接続関係について説明する。ここでは、色素増感太陽電池５０Ｂと色素増感増感太陽電池５０Ｃとの接続関係を例にとって説明する。   Next, the connection relationship between the adjacent dye-sensitized solar cells 50 will be described. Here, the connection relationship between the dye-sensitized solar cell 50B and the dye-sensitized solar cell 50C will be described as an example.

まず色素増感太陽電池５０Ｂについて説明する。   First, the dye-sensitized solar cell 50B will be described.

図３に示すように、色素増感太陽電池５０Ｂにおいて、作用極１０は、透明基板１１及び透明基板１１の上に設けられる透明導電膜１２からなる透明導電性基板１５と、透明導電性基板１５の透明導電膜１２の上に設けられる複数の酸化物半導体層１３と、透明導電膜１２の上において複数の酸化物半導体層１３の各々を包囲するように設けられる配線部１７とを有している。配線部１７は、封止部３０と透明導電膜１２との間に設けられており、透明導電膜１２上に設けられる集電配線１４と、集電配線１４を電解質４０から保護する配線保護層１６とを有している。本実施形態では、透明導電性基板１５によって第１電極が構成されている。   As shown in FIG. 3, in the dye-sensitized solar cell 50 </ b> B, the working electrode 10 includes a transparent substrate 11 and a transparent conductive substrate 15 including a transparent conductive film 12 provided on the transparent substrate 11, and a transparent conductive substrate 15. A plurality of oxide semiconductor layers 13 provided on the transparent conductive film 12 and a wiring portion 17 provided on the transparent conductive film 12 so as to surround each of the plurality of oxide semiconductor layers 13. Yes. The wiring part 17 is provided between the sealing part 30 and the transparent conductive film 12, and the current collector wiring 14 provided on the transparent conductive film 12 and a wiring protective layer that protects the current collector wiring 14 from the electrolyte 40. 16. In the present embodiment, the first electrode is constituted by the transparent conductive substrate 15.

色素増感太陽電池５０Ｂの透明基板１１は、色素増感太陽電池モジュール２００における全色素増感太陽電池５０Ａ〜５０Ｈにおいて共通の透明基板となっている。   The transparent substrate 11 of the dye-sensitized solar cell 50B is a transparent substrate common to all the dye-sensitized solar cells 50A to 50H in the dye-sensitized solar cell module 200.

一方、図２に示すように、色素増感太陽電池５０Ｂの対極２０は、図２の二点鎖線で示される本体部２５と、本体部２５のうち隣りの色素増感太陽電池５０Ｃ側の縁部２５ａの一部から突出する複数の突出部（図２では４つ）２３とを有している。ここで、本体部２５は、金属基板２１と金属基板２１の作用極１０側に設けられて触媒反応を促進する触媒層２２との積層体で構成されている。突出部２３は、金属基板２１のみで構成されている。本実施形態では、対極２０によって第２電極が構成されている。   On the other hand, as shown in FIG. 2, the counter electrode 20 of the dye-sensitized solar cell 50 </ b> B includes a main body portion 25 indicated by a two-dot chain line in FIG. 2 and an edge of the main body portion 25 on the adjacent dye-sensitized solar cell 50 </ b> C side. And a plurality of projecting portions (four in FIG. 2) 23 projecting from a part of the portion 25a. Here, the main body 25 is configured by a laminate of a metal substrate 21 and a catalyst layer 22 that is provided on the working electrode 10 side of the metal substrate 21 and promotes a catalytic reaction. The protrusion 23 is composed of only the metal substrate 21. In the present embodiment, the second electrode is constituted by the counter electrode 20.

次に色素増感太陽電池５０Ｃについて説明する。   Next, the dye-sensitized solar cell 50C will be described.

色素増感太陽電池５０Ｃの作用極１０においては、図４に示すように、集電配線１４が、四角環状の外周部１４ａと、外周部１４ａの内側開口を仕切る複数の仕切り部（フィンガー配線）１４ｂとを有し、外周部１４ａと仕切り部１４ｂとによって酸化物半導体層１３が包囲されている。さらに集電配線１４は、集電配線１４の縁部である外周部１４ａのうち、隣の色素増感太陽電池５０Ｂ側の外周部１４ａの内側に設けられるランド部１４ｃを有している。   In the working electrode 10 of the dye-sensitized solar cell 50C, as shown in FIG. 4, the current collecting wiring 14 has a plurality of partition parts (finger wirings) that partition the rectangular annular outer peripheral part 14a and the inner opening of the outer peripheral part 14a. 14b, and the oxide semiconductor layer 13 is surrounded by the outer peripheral portion 14a and the partition portion 14b. Further, the current collecting wiring 14 has a land portion 14 c provided inside the outer peripheral portion 14 a on the side of the adjacent dye-sensitized solar cell 50 </ b> B in the outer peripheral portion 14 a that is an edge portion of the current collecting wiring 14.

一方、色素増感太陽電池５０Ｃの対極２０においては、ランド部１４ｃに対向する位置に切欠き２４が形成されている（図２参照）。   On the other hand, in the counter electrode 20 of the dye-sensitized solar cell 50C, a notch 24 is formed at a position facing the land portion 14c (see FIG. 2).

そして、図３に示すように、色素増感太陽電池５０Ｃのランド部１４ｃには、色素増感太陽電池５０Ｂの対極２０の突出部２３が直接接続されている。   And as shown in FIG. 3, the protrusion part 23 of the counter electrode 20 of the dye-sensitized solar cell 50B is directly connected to the land part 14c of the dye-sensitized solar cell 50C.

隣り合う２つの色素増感太陽電池５０Ａ，５０Ｂ、隣り合う２つの色素増感太陽電池５０Ｂ，５０Ｃ、２つの色素増感太陽電池５０Ｃ，５０Ｄ、２つの色素増感太陽電池５０Ｅ，５０Ｆ、２つの色素増感太陽電池５０Ｆ，５０Ｇ、２つの色素増感太陽電池５０Ｇ，５０Ｈにおいても同様に、一方の色素増感太陽電池５０における対極２０の突出部２３が、隣りの色素増感太陽電池５０における集電配線１４のランド部１４ｃに直接接続されている。   Two adjacent dye-sensitized solar cells 50A and 50B, two adjacent dye-sensitized solar cells 50B and 50C, two dye-sensitized solar cells 50C and 50D, two dye-sensitized solar cells 50E and 50F, two Similarly, in the dye-sensitized solar cells 50F and 50G and the two dye-sensitized solar cells 50G and 50H, the protrusion 23 of the counter electrode 20 in one of the dye-sensitized solar cells 50 is in the adjacent dye-sensitized solar cell 50. It is directly connected to the land portion 14 c of the current collecting wiring 14.

なお、本実施形態では、色素増感太陽電池５０Ａ〜５０Ｈは全て同一の構成を有している。すなわち、色素増感太陽電池５０Ａ〜５０Ｈにおいて、作用極１０は、封止部３０の外側で且つ集電配線１４の縁部である外周部１４ａよりも内側にランド部２４を有し、対極２０が、本体部２５におけるランド部２４と反対側の縁部２５ａの一部から突出する少なくとも１つの突出部とを有している。そして、図１に示すように、色素増感太陽電池モジュールユニット１００Ａにおいて、色素増感太陽電池５０Ａ〜５０Ｄの各々の対極２０における突出部２３は同一方向（色素増感太陽電池５０Ａから色素増感太陽電池５０Ｄに向かう方向）側に突出している。一方、色素増感太陽電池モジュールユニット１００Ｂにおいて、色素増感太陽電池５０Ｅ〜５０Ｈの各々の対極２０における突出部２３は同一方向（色素増感太陽電池５０Ｅから色素増感太陽電池５０Ｈに向かう方向）側に突出している。但し、色素増感太陽電池モジュールユニット１００Ａ、１００Ｂにおいて、対極２０の突出部２３の突出方向は互いに反対となっている。   In the present embodiment, the dye-sensitized solar cells 50A to 50H all have the same configuration. That is, in the dye-sensitized solar cells 50 </ b> A to 50 </ b> H, the working electrode 10 has the land portion 24 outside the sealing portion 30 and inside the outer peripheral portion 14 a that is the edge of the current collector wiring 14. Has at least one projecting portion projecting from a part of the edge portion 25a opposite to the land portion 24 in the main body portion 25. As shown in FIG. 1, in the dye-sensitized solar cell module unit 100A, the protrusions 23 of the counter electrodes 20 of the dye-sensitized solar cells 50A to 50D are in the same direction (from the dye-sensitized solar cell 50A to the dye-sensitized dye). Projecting toward the solar cell 50D). On the other hand, in the dye-sensitized solar cell module unit 100B, the protrusions 23 of the counter electrodes 20 of the dye-sensitized solar cells 50E to 50H are in the same direction (the direction from the dye-sensitized solar cell 50E toward the dye-sensitized solar cell 50H). Protrudes to the side. However, in the dye-sensitized solar cell module units 100A and 100B, the protruding directions of the protruding portions 23 of the counter electrode 20 are opposite to each other.

また図１に示すように、色素増感太陽電池モジュールユニット１００Ｂにおける色素増感太陽電池５０Ｅ、すなわち、色素増感太陽電池モジュールユニット１００Ｂの端部に配置された色素増感太陽電池５０には、集電配線１４のランド部１４ｃに接続端子７０が設けられている。そして、接続端子７０と、色素増感太陽電池５０Ｄの突出部２３とは、透明基板１１の表面に沿って設けられた導電部材１１０を介して接続されている。この導電部材１１により、色素増感太陽電池モジュールユニット１００Ａと色素増感太陽電池モジュールユニット１００Ｂとが直列に接続される。導電部材１１０を構成する材料としては、例えば銅、銀、ニッケルなどが用いられる。また導電部材１１０の形状としては、テープ状、ワイヤ状などが挙げられるが、テープ状が、使用時に色素増感太陽電池モジュール２００の厚みを小さくすることができることから好ましく用いられる。   Further, as shown in FIG. 1, the dye-sensitized solar cell 50E in the dye-sensitized solar cell module unit 100B, that is, the dye-sensitized solar cell 50 arranged at the end of the dye-sensitized solar cell module unit 100B includes A connection terminal 70 is provided on the land portion 14 c of the current collecting wiring 14. The connection terminal 70 and the protrusion 23 of the dye-sensitized solar cell 50 </ b> D are connected via a conductive member 110 provided along the surface of the transparent substrate 11. The conductive member 11 connects the dye-sensitized solar cell module unit 100A and the dye-sensitized solar cell module unit 100B in series. As a material constituting the conductive member 110, for example, copper, silver, nickel, or the like is used. Further, examples of the shape of the conductive member 110 include a tape shape and a wire shape. The tape shape is preferably used because the thickness of the dye-sensitized solar cell module 200 can be reduced during use.

さらに色素増感太陽電池モジュールユニット１００Ａの色素増感太陽電池５０Ａにも、作用極１０の集電配線１４におけるランド部１４ｃに、接続端子７０が設けられている。   Furthermore, the connection terminal 70 is provided in the land part 14c in the current collection wiring 14 of the working electrode 10 also in the dye-sensitized solar cell 50A of the dye-sensitized solar cell module unit 100A.

次に、上述した色素増感太陽電池モジュール２００の作用効果について説明する。   Next, the effect of the dye-sensitized solar cell module 200 described above will be described.

色素増感太陽電池モジュール２００によれば、突出部２３は、隣り合う２つの色素増感太陽電池５０の一方の色素増感太陽電池５０の対極２０において、本体部２５のうち他方の色素増感太陽電池５０側の縁部２５ａの一部のみから突出し、この突出部２３が、他方の色素増感太陽電池５０のランド部１４ｃに接合されている。このため、開口率を大きく低下させることなく、ランド部１４ｃと突出部２３との接続箇所の面積を十分に大きくすることができる。従って、色素増感太陽電池モジュール２００は、優れた接続信頼性を有する。   According to the dye-sensitized solar cell module 200, the protruding portion 23 is the other dye-sensitized dye of the main body portion 25 in the counter electrode 20 of one dye-sensitized solar cell 50 of two adjacent dye-sensitized solar cells 50. It protrudes from only a part of the edge portion 25a on the solar cell 50 side, and this protruding portion 23 is joined to the land portion 14c of the other dye-sensitized solar cell 50. For this reason, the area of the connection location of the land part 14c and the protrusion part 23 can be enlarged enough, without reducing an aperture ratio largely. Therefore, the dye-sensitized solar cell module 200 has excellent connection reliability.

このように色素増感太陽電池モジュール２００は、本体部２５のうち他方の色素増感太陽電池５０側の縁部２５ａの一部のみから突出する突出部２３と、他方の色素増感太陽電池５０のランド部１４ｃとを接合させることによって優れた接続信頼性を有する。このため、本体部２５のうち他方の色素増感太陽電池５０側の縁部２５ａの残部に突出部２３を設ける必要がない。このため、残部の突出部と他方の色素増感太陽電池５０の透明導電性基板１５とを接続するための接続箇所については省略することが可能となり、開口率を向上させることが可能となる。特に色素増感太陽電池モジュール２００では、ランド部１４ｃが、集電配線１４の縁部である外周部１４ａの内側に設けられている。このため、隣り合う２つの色素増感太陽電池５０の本体部２５同士間の隙間を小さくすることができる。すなわち、発電に寄与しないエリアの面積を小さくすることができる。このため、色素増感太陽電池モジュール２００によれば、ランド部１４ｃが集電配線１４の縁部である外周部１４ａの外側に設けられる場合に比べて開口率を高くすることができる。   As described above, the dye-sensitized solar cell module 200 includes the protruding portion 23 protruding from only a part of the edge portion 25a on the other dye-sensitized solar cell 50 side of the main body portion 25 and the other dye-sensitized solar cell 50. It has excellent connection reliability by joining the land portion 14c. For this reason, it is not necessary to provide the protrusion part 23 in the remaining part of the edge part 25a of the other dye-sensitized solar cell 50 side in the main body part 25. For this reason, it becomes possible to abbreviate | omit about the connection location for connecting the remaining protrusion part and the transparent conductive substrate 15 of the other dye-sensitized solar cell 50, and it becomes possible to improve an aperture ratio. In particular, in the dye-sensitized solar cell module 200, the land portion 14 c is provided inside the outer peripheral portion 14 a that is an edge portion of the current collecting wiring 14. For this reason, the clearance gap between the main-body parts 25 of two adjacent dye-sensitized solar cells 50 can be made small. That is, the area of the area that does not contribute to power generation can be reduced. For this reason, according to the dye-sensitized solar cell module 200, compared with the case where the land part 14c is provided in the outer side of the outer peripheral part 14a which is an edge part of the current collection wiring 14, an aperture ratio can be made high.

さらに、隣り合う２つの色素増感太陽電池５０において、一方の色素増感太陽電池５０においては、ランド部１４ｃに対向する位置に切欠き２４が形成されている。このため、隣り合う２つの色素増感太陽電池５０のうち一方の色素増感太陽電池５０に物体が衝突するなどの理由により、突出部２３がそれに接合されるランド部１４ｃに対して動いたとしても、突出部２３は切欠き２４内に逃げ込むことが可能となる。このため、突出部２３と、隣の色素増感太陽電池５０の対極２０との接触を十分に防止することができる。   Furthermore, in two adjacent dye-sensitized solar cells 50, in one dye-sensitized solar cell 50, a notch 24 is formed at a position facing the land portion 14c. For this reason, it is assumed that the projecting portion 23 moves relative to the land portion 14c joined thereto due to an object colliding with one of the two adjacent dye-sensitized solar cells 50. However, the protrusion 23 can escape into the notch 24. For this reason, the contact between the protrusion 23 and the counter electrode 20 of the adjacent dye-sensitized solar cell 50 can be sufficiently prevented.

また色素増感太陽電池モジュール２００は、色素増感太陽電池モジュールユニット１００Ａ，１００Ｂを有し、色素太陽電池モジュールユニット１００Ａ，１００Ｂが互いに直列且つ電気的に接続されると共に色素増感太陽電池５０の配列方向が互いに平行となるように配列され、色素増感太陽電池モジュールユニット１００Ａ，１００Ｂの各々において、本体部２５に対する突出部２３の突出方向が同一であり、隣り合う２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂにおいて、突出部２３の突出方向が互いに反対となっている。   The dye-sensitized solar cell module 200 includes dye-sensitized solar cell module units 100A and 100B, and the dye solar cell module units 100A and 100B are connected in series and electrically with each other. The dye-sensitized solar cell modules 100A and 100B are arranged so that their arrangement directions are parallel to each other. In each of the dye-sensitized solar cell module units 100A and 100B, the protruding direction of the protruding portion 23 with respect to the main body portion 25 is the same. In the module units 100A and 100B, the protruding directions of the protruding portions 23 are opposite to each other.

このため、隣り合う２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂにおいて、一方の色素増感太陽電池モジュールユニット１００Ｂを構成する色素太陽電池５０のランド部１４ｃと、他方の色素増感太陽電池モジュールユニット１００Ａを構成する色素増感太陽電池５０の突出部２３とを、色素増感太陽電池モジュールユニット１００Ａ，１００Ｂの配列方向に対して同じ側に配置することが可能となる。すなわち、一方の色素増感太陽電池モジュールユニット１００Ｂを構成する色素太陽電池５０のランド部１４ｃと、他方の色素増感太陽電池モジュールユニット１００Ａを構成する色素増感太陽電池５０の突出部２３とを、受光エリア外で接続させることが可能となる。このため、色素増感太陽電池モジュール２００によれば、一方の色素増感太陽電池モジュールユニット１００Ｂを構成する色素太陽電池５０のランド部１４ｃと、他方の色素増感太陽電池モジュールユニット１００Ａを構成する色素増感太陽電池５０の突出部２３とを、開口率を低下させることなく、直列接続させることが可能となる。   Therefore, in two adjacent dye-sensitized solar cell module units 100A and 100B, the land portion 14c of the dye solar cell 50 constituting one dye-sensitized solar cell module unit 100B and the other dye-sensitized solar cell module. It becomes possible to arrange | position the protrusion part 23 of the dye-sensitized solar cell 50 which comprises unit 100A on the same side with respect to the sequence direction of dye-sensitized solar cell module unit 100A, 100B. That is, the land portion 14c of the dye solar cell 50 constituting one dye-sensitized solar cell module unit 100B and the protruding portion 23 of the dye-sensitized solar cell 50 constituting the other dye-sensitized solar cell module unit 100A. It is possible to connect outside the light receiving area. For this reason, according to the dye-sensitized solar cell module 200, the land part 14c of the dye solar cell 50 which comprises one dye-sensitized solar cell module unit 100B, and the other dye-sensitized solar cell module unit 100A are comprised. The protrusion 23 of the dye-sensitized solar cell 50 can be connected in series without reducing the aperture ratio.

次に、上記色素増感太陽電池モジュール２００の製造方法について説明する。   Next, the manufacturing method of the said dye-sensitized solar cell module 200 is demonstrated.

まず図３に示すように、１つの透明基板１１の上に、透明導電膜１２を形成してなる透明導電性基板１５を用意する。   First, as shown in FIG. 3, a transparent conductive substrate 15 formed by forming a transparent conductive film 12 on one transparent substrate 11 is prepared.

透明基板１１を構成する材料は、例えば透明な材料であればよく、このような透明な材料としては、例えばホウケイ酸ガラス、ソーダライムガラス、白板ガラス、石英ガラスなどのガラス、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリカーボネート（ＰＣ）、ポリエーテルスルフォン（ＰＥＳ）などが挙げられる。透明基板９の厚さは、色素増感太陽電池１００のサイズに応じて適宜決定され、特に限定されるものではないが、例えば５０μｍ〜１００００μｍの範囲にすればよい。   The material which comprises the transparent substrate 11 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES) and the like. The thickness of the transparent substrate 9 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be in the range of 50 μm to 10000 μm, for example.

透明導電膜１２を構成する材料としては、例えばスズ添加酸化インジウム（Indium−Tin−Oxide：ＩＴＯ）、酸化スズ（ＳｎＯ２）、フッ素添加酸化スズ（Fluorine−doped−Tin−Oxide：ＦＴＯ）などの導電性金属酸化物が挙げられる。透明導電膜１２は、単層でも、異なる導電性金属酸化物で構成される複数の層の積層体で構成されてもよい。透明導電膜１２が単層で構成される場合、透明導電膜１２は、高い耐熱性及び耐薬品性を有することから、ＦＴＯで構成されることが好ましい。また透明導電膜１０として、複数の層で構成される積層体を用いると、各層の特性を反映させることが可能となることから好ましい。中でも、ＩＴＯで構成される層と、ＦＴＯで構成される層との積層体を用いることが好ましい。この場合、高い導電性、耐熱性及び耐薬品性を持つ透明導電膜１２が実現できる。透明導電膜１２の厚さは例えば０．０１μｍ〜２μｍの範囲にすればよい。 As a material constituting the transparent conductive film 12, for example, tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO 2 ), fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO), etc. Examples include conductive metal oxides. The transparent conductive film 12 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 12 is composed of a single layer, the transparent conductive film 12 is preferably composed of FTO because it has high heat resistance and chemical resistance. In addition, it is preferable to use a laminate composed of a plurality of layers as the transparent conductive film 10 because the characteristics of each layer can be reflected. Among these, it is preferable to use a laminate of a layer made of ITO and a layer made of FTO. In this case, the transparent conductive film 12 having high conductivity, heat resistance and chemical resistance can be realized. The thickness of the transparent conductive film 12 may be in the range of 0.01 μm to 2 μm, for example.

透明導電膜１２の形成方法としては、スパッタ法、蒸着法、スプレー熱分解法（ＳＰＤ：Spray Pyrolysis Deposition）及びＣＶＤ法などが用いられる。これらのうちスプレー熱分解法が装置コストの点から好ましい。   As a method for forming the transparent conductive film 12, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used. Of these, the spray pyrolysis method is preferable from the viewpoint of apparatus cost.

次に、レーザ加工又はエッチング等により、透明導電膜１２を、互いに離間した複数の透明導電膜１２に分割する。   Next, the transparent conductive film 12 is divided into a plurality of transparent conductive films 12 separated from each other by laser processing or etching.

次に、分割された複数の透明導電膜１２の各々の上に酸化物半導体層１３を形成する。酸化物半導体層１３は、酸化物半導体粒子を含む多孔質酸化物半導体層形成用ペーストを印刷した後、焼成して形成する。   Next, the oxide semiconductor layer 13 is formed on each of the divided transparent conductive films 12. The oxide semiconductor layer 13 is formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles, followed by firing.

酸化物半導体層形成用ペーストは、酸化物半導体粒子のほか、ポリエチレングリコールなどの樹脂及び、テレピネオールなどの溶媒を含む。酸化物半導体粒子は、例えば酸化チタン（ＴｉＯ2）、シリカ（ＳｉＯ2）、酸化亜鉛（ＺｎＯ）、酸化タングステン（ＷＯ3）、酸化ニオブ（Ｎｂ2Ｏ5）、チタン酸ストロンチウム（ＳｒＴiＯ3）、酸化スズ（ＳｎＯ2）、酸化インジウム（Ｉｎ３Ｏ３）、酸化ジルコニウム（ＺｒＯ２）、酸化タリウム（Ｔａ２Ｏ５）、酸化ランタン（Ｌａ２Ｏ３）、酸化イットリウム（Ｙ２Ｏ３）、酸化ホルミウム（Ｈｏ２Ｏ３）、酸化ビスマス（Ｂｉ２Ｏ３）、酸化セリウム（ＣｅＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）又はこれらの２種以上で構成される。 The oxide semiconductor layer forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO 2 ), silica (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), strontium titanate (SrTiO 3 ), Tin oxide (SnO 2 ), indium oxide (In 3 O 3 ), zirconium oxide (ZrO 2 ), thallium oxide (Ta 2 O 5 ), lanthanum oxide (La 2 O 3 ), yttrium oxide (Y 2 O 3 ), It consists of holmium oxide (Ho 2 O 3 ), bismuth oxide (Bi 2 O 3 ), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), or two or more thereof.

酸化物半導体層１３の厚さは、例えば０．５〜５０μｍとすればよい。   The thickness of the oxide semiconductor layer 13 may be, for example, 0.5 to 50 μm.

酸化物半導体層形成用ペーストの印刷方法としては、例えばスクリーン印刷法、ドクターブレード法、バーコート法などを用いることができる。   As a method for printing the oxide semiconductor layer forming paste, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

焼成温度は酸化物半導体粒子の材質により異なるが、通常は３５０℃〜６００℃であり、焼成時間も、酸化物半導体粒子の材質により異なるが、通常は１〜５時間である。   The firing temperature varies depending on the material of the oxide semiconductor particles, but is usually 350 ° C. to 600 ° C., and the firing time also varies depending on the material of the oxide semiconductor particles, but is usually 1 to 5 hours.

次に、透明導電膜１２上に、銀などの導電材料を含むペーストを塗布する。このとき、ペーストの塗布は、図４に示すように、外周部１４ａと、外周部１４ａの内側開口を仕切る仕切り部１４ｂと、外周部１４ａの内側に設けられるランド部１４ｃを形成するように行う。そして、ペーストを焼成して集電配線１４が得られる。   Next, a paste containing a conductive material such as silver is applied on the transparent conductive film 12. At this time, as shown in FIG. 4, the paste is applied so as to form an outer peripheral portion 14a, a partition portion 14b that partitions the inner opening of the outer peripheral portion 14a, and a land portion 14c provided inside the outer peripheral portion 14a. . And the current collection wiring 14 is obtained by baking the paste.

次に、集電配線１４を低融点ガラスフリットなどの配線保護層１６で被覆する。このとき、配線保護層１６は、外周部１４ａ及び仕切り部１４ｂを覆い、ランド部１４ｃを覆わないようにする。こうして集電配線１４と配線保護層１６とによって配線部１７が得られる。   Next, the current collector wiring 14 is covered with a wiring protective layer 16 such as a low melting point glass frit. At this time, the wiring protective layer 16 covers the outer peripheral portion 14a and the partition portion 14b and does not cover the land portion 14c. Thus, the wiring portion 17 is obtained by the current collecting wiring 14 and the wiring protective layer 16.

こうして複数の作用極１０が得られる。   Thus, a plurality of working electrodes 10 are obtained.

次に、色素増感太陽電池５０の数と同数の封止部３０を準備する。各封止部３０としては、酸化物半導体層１３を包囲する開口が形成されたものを用いる。   Next, the same number of sealing portions 30 as the number of dye-sensitized solar cells 50 are prepared. As each sealing part 30, what formed the opening surrounding the oxide semiconductor layer 13 is used.

封止部３０としては、例えばアイオノマー、エチレン−ビニル酢酸無水物共重合体、エチレン−メタクリル酸共重合体、エチレン−ビニルアルコール共重合体、紫外線硬化樹脂、及び、ビニルアルコール重合体などの樹脂が挙げられる。   Examples of the sealing unit 30 include resins such as ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ultraviolet curable resins, and vinyl alcohol polymers. Can be mentioned.

そして、この封止部３０を作用極１０の集電配線１４の上に接着させる。このとき、同一形状の封止部３０を対極２０の表面に接着させてもよい。封止部３０の集電配線１４又は対極２０への接着は、封止部３０を加熱溶融させることによって行うことができる。このとき、集電配線１４のランド部１４ｃには、その封止部３０の外周部にのみを接着させるようにする。   Then, the sealing portion 30 is bonded onto the current collecting wiring 14 of the working electrode 10. At this time, the sealing portion 30 having the same shape may be adhered to the surface of the counter electrode 20. Adhesion of the sealing portion 30 to the current collector wiring 14 or the counter electrode 20 can be performed by heating and melting the sealing portion 30. At this time, only the outer peripheral portion of the sealing portion 30 is adhered to the land portion 14 c of the current collecting wiring 14.

次に、複数の作用極１０の酸化物半導体層１３に光増感色素を担持させる。このためには、作用極１０を、光増感色素を含有する溶液の中に浸漬させ、その色素を酸化物半導体層１３に吸着させた後に上記溶液の溶媒成分で余分な色素を洗い流し、乾燥させることで、光増感色素を酸化物半導体層１３に吸着させればよい。但し、光増感色素を含有する溶液を酸化物半導体層１３に塗布した後、乾燥させることによって光増感色素を酸化物半導体層１３に吸着させても、光増感色素を酸化物半導体層１３に担持させることが可能である。   Next, a photosensitizing dye is supported on the oxide semiconductor layers 13 of the plurality of working electrodes 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, the dye is adsorbed on the oxide semiconductor layer 13, and then the excess dye is washed away with the solvent component of the solution, followed by drying. Thus, the photosensitizing dye may be adsorbed to the oxide semiconductor layer 13. However, even if the photosensitizing dye is adsorbed to the oxide semiconductor layer 13 by applying a solution containing the photosensitizing dye to the oxide semiconductor layer 13 and then drying the solution, the photosensitizing dye can be absorbed into the oxide semiconductor layer 13. 13 can be carried.

光増感色素としては、例えばビピリジン構造、ターピリジン構造などを含む配位子を有するルテニウム錯体や、ポルフィリン、エオシン、ローダミン、メロシアニンなどの有機色素が挙げられる。   Examples of the photosensitizing dye include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine.

次に、複数の作用極１０の酸化物半導体層１３の上に電解質４０を配置する。電解質４０は、例えばスクリーン印刷等の印刷法によって配置することが可能である。   Next, the electrolyte 40 is disposed on the oxide semiconductor layers 13 of the plurality of working electrodes 10. The electrolyte 40 can be disposed by a printing method such as screen printing.

電解質４０は例えばＩ−／Ｉ３ −などの酸化還元対と有機溶媒とを含んでいる。有機溶媒としては、アセトニトリル、メトキシアセトニトリル、メトキシプロピオニトリル、プロピオニトリル、エチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート、γ−ブチロラクトンなどを用いることができる。酸化還元対としては、例えばＩ−／Ｉ３ −のほか、臭素／臭化物イオンなどの対が挙げられる。なお、上記揮発性溶媒にはゲル化剤を加えてもよい。また電解質４０は、イオン液体と揮発性成分との混合物からなるイオン液体電解質で構成されてもよい。イオン液体としては、例えばピリジニウム塩、イミダゾリウム塩、トリアゾリウム塩等の既知のヨウ素塩であって、室温付近で溶融状態にある常温溶融塩が用いられる。このような常温溶融塩としては、例えば１−エチル−３−メチルイミダゾリウム ビス（トリフルオロメチルスルホニル）イミドが好適に用いられる。また揮発性成分としては、上記の有機溶媒や、１−メチル−３−メチルイミダゾリウムヨーダイド、ＬｉＩ、Ｉ２、４−ｔ−ブチルピリジンなどが挙げられる。 The electrolyte 40 contains a redox couple such as I − / I 3 — and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, and the like can be used. Examples of the redox pair include I − / I 3 − and bromine / bromide ion pairs. A gelling agent may be added to the volatile solvent. The electrolyte 40 may be composed of an ionic liquid electrolyte made of a mixture of an ionic liquid and a volatile component. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. As such a room temperature molten salt, for example, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is preferably used. As the volatile component, the above and an organic solvent, 1-methyl-3-methyl imidazolium iodide, LiI, and the like I 2, 4-t-butylpyridine.

次に、複数の対極２０を用意し、複数の対極２０の各々を、封止部３０の開口を塞ぐように貼り合わせる。   Next, a plurality of counter electrodes 20 are prepared, and each of the plurality of counter electrodes 20 is bonded so as to close the opening of the sealing portion 30.

対極２０は、上述したように、本体部２５と、本体部２５のうち隣の色素増感太陽電池５０側の縁部２５ａの一部から突出する４つの突出部２３とを備える。ここで、本体部２５は、金属基板２１と触媒層２２との積層体で構成され、突出部２３は金属基板２１のみで構成されている。但し、突出部２３も金属基板２１と触媒層２２との積層体で構成されてもよい。   As described above, the counter electrode 20 includes the main body 25 and the four protrusions 23 protruding from a part of the edge 25 a on the side of the adjacent dye-sensitized solar cell 50 in the main body 25. Here, the main body portion 25 is configured by a laminate of the metal substrate 21 and the catalyst layer 22, and the protruding portion 23 is configured by only the metal substrate 21. However, the protrusion 23 may also be formed of a laminate of the metal substrate 21 and the catalyst layer 22.

金属基板２１は、例えばチタン、ニッケル、白金、モリブデン、タングステン等の耐食性を有し且つ不動態膜を有する金属で構成される。   The metal substrate 21 is made of a metal having a corrosion resistance and having a passive film, such as titanium, nickel, platinum, molybdenum, and tungsten.

触媒層２２は、白金、炭素系材料又は導電性高分子などから構成される。ここで、炭素系材料としては、カーボンナノチューブが好適に用いられる。   The catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like. Here, carbon nanotubes are suitably used as the carbon-based material.

次に、対極２０の突出部２３を、隣の色素増感太陽電池５０の作用極１０における集電配線１４のランド部１４ｃに接続する。ランド部１４ｃへの突出部２３の接続は、例えば抵抗溶接によって行うことができる。図５に示すように、抵抗溶接は、２本の抵抗溶接用電極１１０Ａ，１１０Ｂを突出部２３及びランド部１４ｃ又はそのいずれか一方に押し当てて両者間に電流を流すことにより、ランド部１４ｃと金属基板２１との接触部分で熱を発生させ、この熱によりランド部１４ｃ及び突出部２３の両方を溶融させて両者を接続させる方法である。このとき、熱はランド部１４ｃと突出部２３の接触部分のみにしか発生しない。また、抵抗溶接においては通常、電流を流す時間は短時間（数ミリ秒）であるため、熱が発生する時間も短い。このため、熱が加えられる場所を局所領域に抑えることができる。従って、封止工程の後、対極２０の突出部２３をランド部１４ｃに接合する場合でも、酸化物半導体層１３に担持された光増感色素の劣化を十分に抑制することができる。   Next, the protruding portion 23 of the counter electrode 20 is connected to the land portion 14 c of the current collecting wiring 14 in the working electrode 10 of the adjacent dye-sensitized solar cell 50. The connection of the protruding portion 23 to the land portion 14c can be performed by resistance welding, for example. As shown in FIG. 5, in resistance welding, the two resistance welding electrodes 110A and 110B are pressed against the projecting portion 23 and / or the land portion 14c, and an electric current is passed between them, thereby causing the land portion 14c to flow. In this method, heat is generated at a contact portion between the metal substrate 21 and the metal substrate 21, and both the land portion 14c and the protruding portion 23 are melted by this heat to connect the two. At this time, heat is generated only in the contact portion between the land portion 14 c and the protruding portion 23. In resistance welding, the current is usually supplied for a short time (several milliseconds), so the time for generating heat is also short. For this reason, the place where heat is applied can be suppressed to a local region. Therefore, even when the protruding portion 23 of the counter electrode 20 is joined to the land portion 14c after the sealing step, deterioration of the photosensitizing dye supported on the oxide semiconductor layer 13 can be sufficiently suppressed.

またこのとき、突出部２３に含まれる金属基板２１は不動態膜を有するため、ランド部１４ｃの抵抗が金属基板２１より低いと、金属基板２１とランド部１４ｃとの間での接触抵抗が大きくなる。このため、金属基板２１とランド部１４ｃとが互いに接触する部分が熱により溶融しやすくなる。そして、２本の電極１１０Ａ，１１０Ｂの間に印加する電圧をオフにすると、図６に示すように、溶融した部分が凝固して合金部６０を形成する。従って、突出部２３とランド部１４ｃとの接合強度を十分に向上させることができる。また対極２０の突出部２３とランド部１４ｃとの間に合金部６０が設けられることで、対極２０の突出部２３と集電配線１４のランド部１４ｃとの間の接触抵抗も低下させることができる。   At this time, since the metal substrate 21 included in the protruding portion 23 has a passive film, if the resistance of the land portion 14c is lower than that of the metal substrate 21, the contact resistance between the metal substrate 21 and the land portion 14c is large. Become. For this reason, the portion where the metal substrate 21 and the land portion 14c are in contact with each other is easily melted by heat. When the voltage applied between the two electrodes 110A and 110B is turned off, the melted portion is solidified to form the alloy portion 60 as shown in FIG. Accordingly, the bonding strength between the protruding portion 23 and the land portion 14c can be sufficiently improved. Further, by providing the alloy part 60 between the protruding part 23 of the counter electrode 20 and the land part 14 c, the contact resistance between the protruding part 23 of the counter electrode 20 and the land part 14 c of the current collector wiring 14 can be reduced. it can.

また対極２０の突出部２３とランド部１４ｃとを抵抗溶接により接続する際に、抵抗溶接を、ランド部１４ｃと突出部２３とを接触させた状態で、２つの抵抗溶接用の電極１１０Ａ，１１０Ｂを、突出部２３のうちランド部１４ｃと反対側の表面に当接させることによって行うことが好ましい。   When the protrusion 23 and the land 14c of the counter electrode 20 are connected by resistance welding, the resistance welding is performed in a state where the land 14c and the protrusion 23 are in contact with each other, and the two electrodes 110A and 110B for resistance welding are used. Is preferably performed by contacting the surface of the protruding portion 23 on the side opposite to the land portion 14c.

この場合、対極２０と集電配線１４とを抵抗溶接により接続する際に、２つの抵抗溶接用電極を集電配線１４及び対極２０の金属基板２１のうち作用極１０側の表面に押し当てずに済む。このため、対極２０の金属基板２１のうち作用極１０側の表面に、抵抗溶接用電極の溶着による不純物を介在させないという利点が得られる。また、集電配線１４に抵抗溶接用電極を押し当てずに済むので、省スペースにおいて、溶接することが出来る。   In this case, when the counter electrode 20 and the current collector wire 14 are connected by resistance welding, the two resistance welding electrodes are not pressed against the surface of the current collector wire 14 and the metal substrate 21 of the counter electrode 20 on the working electrode 10 side. It will end. For this reason, the advantage that the impurity by welding of the electrode for resistance welding is not interposed in the surface by the side of the working electrode 10 among the metal substrates 21 of the counter electrode 20 is acquired. In addition, since it is not necessary to press the resistance welding electrode against the current collector wiring 14, welding can be performed in a small space.

また抵抗溶接は3〜20ミリ秒行うことが好ましく、5〜7ミリ秒行うことがより好ましい。この場合、対極２０と集電配線１４との接続強度をより十分に向上させることができると共に、合金部６０の厚さが適度になり、集電配線１４のランド部１４ｃと突出部２３との間の抵抗をより十分に低くすることができる。   Resistance welding is preferably performed for 3 to 20 milliseconds, more preferably 5 to 7 milliseconds. In this case, the connection strength between the counter electrode 20 and the current collector wiring 14 can be improved more sufficiently, and the thickness of the alloy part 60 becomes appropriate, so that the land 14c and the protrusion 23 of the current collector wiring 14 The resistance between them can be made sufficiently lower.

対極２０の厚さは特に制限されるものではないが、9〜200μｍであることが好ましく、9〜200μｍであることがより好ましく、20〜100μｍであることがより好ましい。対極２０の厚さが9μｍ以上であると、9μｍ未満である場合に比べて強度がより大きくなり、抵抗溶接に際して変形しにくくなる。一方、対極２０の厚さが、200μｍ以下であると、200μｍを超える場合に比べて、より短時間で対極２０の突出部２３とランド部１４ｃとを接続できる。また対極２０に可撓性を持たせることもできる。   The thickness of the counter electrode 20 is not particularly limited, but is preferably 9 to 200 μm, more preferably 9 to 200 μm, and more preferably 20 to 100 μm. When the thickness of the counter electrode 20 is 9 μm or more, the strength is greater than when the thickness is less than 9 μm, and deformation during resistance welding is difficult. On the other hand, when the thickness of the counter electrode 20 is 200 μm or less, the protruding portion 23 of the counter electrode 20 and the land portion 14 c can be connected in a shorter time than when the counter electrode 20 exceeds 200 μm. Further, the counter electrode 20 can be flexible.

集電配線１４のランド部１４ｃの厚さも特に制限されるものではないが、0.1〜50μｍであることが好ましく、1〜30μｍであることがより好ましい。   The thickness of the land portion 14c of the current collecting wiring 14 is not particularly limited, but is preferably 0.1 to 50 μm, and more preferably 1 to 30 μm.

この場合、集電配線１４のランド部１４ｃの厚さが0.1μｍ以上であると、0.1μｍ未満である場合に比べて強度がより大きくなり、抵抗溶接に際して変形しにくくなる。一方、集電配線１４のランド部１４ｃの厚さが、50μｍ以下であると、50μｍを超える場合に比べてより短時間で対極２０の突出部２３とランド部１４ｃとを接続できる。   In this case, when the thickness of the land portion 14c of the current collecting wiring 14 is 0.1 μm or more, the strength is greater than when the thickness is less than 0.1 μm, and deformation during resistance welding is difficult. On the other hand, when the thickness of the land portion 14c of the current collector wiring 14 is 50 μm or less, the protruding portion 23 of the counter electrode 20 and the land portion 14c can be connected in a shorter time than when the land portion 14c exceeds 50 μm.

また対極２０の突出部２３とランド部１４ｃとを溶融させて接合させるため、両者の間に合金部が形成される。このため、金属基板２１と集電配線１４との接合強度が大きくなり、得られた複数の色素増感太陽電池５０を直列に接続した場合に、優れた接続信頼性を有する色素増感太陽電池モジュール１００を得ることができる。また対極第２電極と集電配線との間に合金部が設けられることで、第２電極と集電配線との間の接触抵抗も低下させることができる。従って、得られる色素増感太陽電池モジュールは、優れた導電性も有することとなる。   Moreover, since the protrusion part 23 and the land part 14c of the counter electrode 20 are melted and joined, an alloy part is formed between them. For this reason, the bonding strength between the metal substrate 21 and the current collector wiring 14 is increased, and when the obtained dye-sensitized solar cells 50 are connected in series, the dye-sensitized solar cell having excellent connection reliability. A module 100 can be obtained. Moreover, the contact resistance between a 2nd electrode and current collection wiring can also be reduced by providing an alloy part between the counter electrode 2nd electrode and current collection wiring. Therefore, the obtained dye-sensitized solar cell module also has excellent conductivity.

２つの抵抗溶接用電極１１０Ａ，１１０Ｂ間に印加する電流は、対極２０の突出部２３とランド部１４ｃとの組合せにも依存するため一概には言えないが、通常は0.01〜3kAであり、0.1〜2kAであることが好ましい。   The current applied between the two resistance welding electrodes 110A and 110B depends on the combination of the protruding portion 23 and the land portion 14c of the counter electrode 20, and thus cannot be generally stated, but is usually 0.01 to 3 kA, 0.1 It is preferably ˜2 kA.

また電流の印加時間も一概には言えないが、通常は3〜20ミリ秒であり、5〜7ミリ秒であることが好ましい。   Also, the current application time cannot be generally specified, but it is usually 3 to 20 milliseconds, preferably 5 to 7 milliseconds.

さらに抵抗溶接用電極１１０Ａ，１１０Ｂ間の間隔も一概には言えないが、通常は、0.3〜20ｍｍであり、0.5〜10ｍｍであることが好ましい。   Furthermore, the distance between the resistance welding electrodes 110A and 110B cannot be generally specified, but is usually 0.3 to 20 mm, and preferably 0.5 to 10 mm.

こうして色素増感太陽電池モジュールユニット１００Ａ，１００Ｂが得られる。   Thus, dye-sensitized solar cell module units 100A and 100B are obtained.

次に、色素増感太陽電池５０Ａ，５０Ｅの集電配線１４におけるランド部１４ｃにそれぞれ接続端子７０を接続する。接続端子７０は、銀，銅，ニッケルなどの部材を抵抗溶接法などの方法を用いてランド部１４ｃに接続することができる。なお、接続端子７０は、集電配線１４を形成する際に、集電配線１４と同様の材料を用い、スクリーン印刷法で集電配線１４と同時に形成されてもよい。   Next, the connection terminals 70 are connected to the land portions 14c in the current collecting wiring 14 of the dye-sensitized solar cells 50A and 50E, respectively. The connection terminal 70 can connect a member such as silver, copper, or nickel to the land portion 14c using a method such as resistance welding. The connection terminal 70 may be formed simultaneously with the current collector wiring 14 by a screen printing method using the same material as that for the current collector wiring 14 when the current collector wiring 14 is formed.

最後に、導電部材１１０を接続端子７０に接続する。導電部材１１０は、例えば抵抗溶接によって接続端子７０と接続することができる。   Finally, the conductive member 110 is connected to the connection terminal 70. The conductive member 110 can be connected to the connection terminal 70 by, for example, resistance welding.

以上のようにして色素増感太陽電池２００が得られる。   The dye-sensitized solar cell 200 is obtained as described above.

＜第２実施形態＞
次に、本発明の色素増感太陽電池モジュールの第２実施形態について説明する。なお、第１実施形態と同一又は同等の構成要素には同一符号を付し、重複する説明を省略する。 Second Embodiment
Next, a second embodiment of the dye-sensitized solar cell module of the present invention will be described. In addition, the same code | symbol is attached | subjected to the component same or equivalent to 1st Embodiment, and the overlapping description is abbreviate | omitted.

図７は、本発明の色素増感太陽電池モジュールの第２実施形態を示す一部切欠き部分平面図、図８は、図７のＶＩＩＩ−ＶＩＩＩ線に沿った断面図である。本実施形態の色素増感太陽電池モジュール３００は、対極の点で第１実施形態の色素増感太陽電池モジュール２００と相違する。   FIG. 7 is a partially cutaway partial plan view showing a second embodiment of the dye-sensitized solar cell module of the present invention, and FIG. 8 is a cross-sectional view taken along line VIII-VIII in FIG. The dye-sensitized solar cell module 300 of this embodiment is different from the dye-sensitized solar cell module 200 of the first embodiment in terms of the counter electrode.

すなわち、図７及び図８に示すように、本実施形態の色素増感太陽電池モジュール３００において、対極３２０は、金属基板２１及び触媒層２２に加えて、金属基板２１のうち作用極１０と反対側の表面に設けられる複数の線状の導電材３３０を更に有している。この導電材３３０は、金属基板２１よりも低い抵抗を有する金属からなる。このような金属は、金属基板２１よりも低い抵抗を有する金属であればよく、このような金属としては、例えば銅が用いられる。そして、導電部材３３０の端部が突出部２３として、隣の色素増感太陽電池５０の作用極１０の集電配線１４におけるランド部１４ｃに直接接続されている。ここで、導電材３３０とランド部１４ｃとの間には、導電材３３０を構成する金属と、ランド部１４ｃを構成する金属との合金部が設けられている。   That is, as shown in FIGS. 7 and 8, in the dye-sensitized solar cell module 300 of the present embodiment, the counter electrode 320 is opposite to the working electrode 10 of the metal substrate 21 in addition to the metal substrate 21 and the catalyst layer 22. It further has a plurality of linear conductive materials 330 provided on the side surface. The conductive material 330 is made of a metal having a lower resistance than the metal substrate 21. Such a metal should just be a metal which has resistance lower than the metal substrate 21, and copper is used as such a metal, for example. And the edge part of the electrically-conductive member 330 is directly connected to the land part 14c in the current collection wiring 14 of the working electrode 10 of the adjacent dye-sensitized solar cell 50 as the protrusion part 23. FIG. Here, between the conductive material 330 and the land portion 14c, an alloy portion of the metal constituting the conductive material 330 and the metal constituting the land portion 14c is provided.

この場合、対極３２０の導電材３３０と、集電配線１４との間に、対極３２０における導電材３３０を構成する金属と、集電配線１４を構成する金属との合金からなる合金部が設けられているため、対極３２０と集電配線１４との接続強度が大きくなり、優れた接続信頼性が得られる。また対極３２０の導電材３３０と集電配線１４との間に合金部が設けられることで、対極３２０と集電配線１４との間の接触抵抗も低下させることができる。このため、色素増感太陽電池５０同士間において十分に小さい抵抗で接続することが可能になり、電圧降下がほとんど起こらない。またランド部１４ｃから流れ込む電子を、金属基板２１より抵抗の低い導電材３３０を通して電解質４０に近づけることが可能となるため、導電材３３０から電解質４０までの抵抗を小さくすることも可能となる。   In this case, an alloy portion made of an alloy of the metal constituting the conductive material 330 in the counter electrode 320 and the metal constituting the current collector wiring 14 is provided between the conductive material 330 of the counter electrode 320 and the current collector wiring 14. Therefore, the connection strength between the counter electrode 320 and the current collector wiring 14 is increased, and excellent connection reliability is obtained. Moreover, the contact resistance between the counter electrode 320 and the current collector wiring 14 can be reduced by providing the alloy part between the conductive material 330 of the counter electrode 320 and the current collector wiring 14. For this reason, it becomes possible to connect between the dye-sensitized solar cells 50 with a sufficiently small resistance, and a voltage drop hardly occurs. In addition, since electrons flowing from the land portion 14 c can be brought closer to the electrolyte 40 through the conductive material 330 having a lower resistance than that of the metal substrate 21, the resistance from the conductive material 330 to the electrolyte 40 can be reduced.

このとき、対極３２０の突出部２３とランド部１４ｃとの接続は、抵抗溶接により行う。   At this time, the connection between the protruding portion 23 of the counter electrode 320 and the land portion 14c is performed by resistance welding.

この場合、隣り合う２つの色素増感太陽電池５０のうち一方の色素増感太陽電池５０の対極３２０の突出部２３と、他方の色素増感太陽電池５０の集電配線１４のランド部１４ｃとを、はんだ等を用いることなく、簡便に接合させることができるとともに、接続強度を向上させることがき、接触抵抗も低下させることができる。また、抵抗溶接は、一方の色素増感太陽電池５０Ａの導電材３３０と、他方の色素増感太陽電池５０Ｂのランド部１４ｃとを接合する際、抵抗溶接用の電極を局所的に当てて行うため、熱が局所的にしか発生しない。このため、はんだ等を用いて接合を行う場合に比べて、酸化物半導体層１３に担持された色素や封止部の劣化がより十分に抑制される。なお、突出部２３とランド部１４ｃとの抵抗溶接も、上記と同様、２つの抵抗溶接用電極をいずれも突出部２３のうちランド部１４ｃと反対側の表面に押し当てて、２つの抵抗溶接用電極間に電圧を印加すればよい。   In this case, of the two adjacent dye-sensitized solar cells 50, the protruding portion 23 of the counter electrode 320 of one dye-sensitized solar cell 50, and the land portion 14 c of the current collecting wiring 14 of the other dye-sensitized solar cell 50 Can be simply joined without using solder or the like, the connection strength can be improved, and the contact resistance can also be reduced. Resistance welding is performed by locally applying an electrode for resistance welding when joining the conductive material 330 of one dye-sensitized solar cell 50A and the land portion 14c of the other dye-sensitized solar cell 50B. Therefore, heat is generated only locally. For this reason, compared with the case where it joins using solder etc., degradation of the pigment carried by oxide semiconductor layer 13 and a sealing part is controlled more fully. In the resistance welding between the protruding portion 23 and the land portion 14c, the two resistance welding electrodes are pressed against the surface of the protruding portion 23 opposite to the land portion 14c in the same manner as described above. A voltage may be applied between the working electrodes.

また対極３２０を作製する際には、導電材３３０と、金属基板２１とを抵抗溶接によって接合することが好ましい。具体的にはまず、導電材３３０のうちランド部１４ｃと反対側の表面に、２つの抵抗溶接用電極の両方を押し当て、２つの抵抗溶接用電極間に電圧を印加すればよい。   Moreover, when producing the counter electrode 320, it is preferable to join the electrically conductive material 330 and the metal substrate 21 by resistance welding. Specifically, first, both the two resistance welding electrodes may be pressed against the surface of the conductive material 330 opposite to the land portion 14c to apply a voltage between the two resistance welding electrodes.

このように対極３２０の金属基板２１に導電材３３０を形成する場合でも、酸化物半導体層１３に担持された光増感色素や封止部の劣化を十分に抑制することができる。さらに得られる色素増感太陽電池モジュール２００の導電性及び接続信頼性をより向上させることができる。   As described above, even when the conductive material 330 is formed on the metal substrate 21 of the counter electrode 320, deterioration of the photosensitizing dye and the sealing portion carried on the oxide semiconductor layer 13 can be sufficiently suppressed. Furthermore, the electroconductivity and connection reliability of the obtained dye-sensitized solar cell module 200 can be further improved.

本発明は、上記実施形態に限定されるものではない。例えば上記第１実施形態では、対極２０の金属基板２１が突出部２３として、隣の色素増感太陽電池５０の集電配線１４におけるランド部１４ｃに直接接続されているが、図９に示すように、突出部２３は、インサート材４００を介して隣の色素増感太陽電池５０の集電配線１４におけるランド部１４ｃに接続されてもよい。この場合、突出部２３とインサート材４００との間に、金属基板２１を構成する金属と、インサート材４００を構成する金属との合金からなる合金部が設けられる。ここで、インサート材４００としては、金属基板２１及び集電配線１４よりも低い抵抗を有するものを用いることが好ましい。この場合、抵抗溶接によって突出部２３とランド部１４ｃとを接続する際、突出部２３とインサート材４００とが接合しやすく、インサート材４００と集電配線１４とが接合しやすくなる。   The present invention is not limited to the above embodiment. For example, in the first embodiment, the metal substrate 21 of the counter electrode 20 is directly connected as the projecting portion 23 to the land portion 14c in the current collecting wiring 14 of the adjacent dye-sensitized solar cell 50, as shown in FIG. In addition, the protruding portion 23 may be connected to the land portion 14 c in the current collecting wiring 14 of the adjacent dye-sensitized solar cell 50 through the insert material 400. In this case, an alloy portion made of an alloy of the metal constituting the metal substrate 21 and the metal constituting the insert material 400 is provided between the protruding portion 23 and the insert material 400. Here, it is preferable to use a material having a lower resistance than the metal substrate 21 and the current collector wiring 14 as the insert material 400. In this case, when connecting the protrusion part 23 and the land part 14c by resistance welding, the protrusion part 23 and the insert material 400 are easily joined, and the insert material 400 and the current collector wiring 14 are easily joined.

また上記第１及び第２実施形態では、色素増感太陽電池モジュール２００，３００は、２つの色素増感太陽電池モジュールユニット１００Ａ，１００Ｂを有しているが、２つに限られず、１つでもよいし、３つ以上でもよい。また上記第１及び第２実施形態では、色素増感太陽電池モジュールユニット１００Ａ，１００Ｂにおいて色素増感太陽電池５０を４つ備えているが、色素増感太陽電池５０の数は４つに限られず、複数であればいかなる数であってもよい。   In the first and second embodiments, the dye-sensitized solar cell modules 200 and 300 include two dye-sensitized solar cell module units 100A and 100B, but the number is not limited to two. It may be three or more. In the first and second embodiments, the dye-sensitized solar cell module units 100A and 100B include four dye-sensitized solar cells 50. However, the number of dye-sensitized solar cells 50 is not limited to four. Any number is acceptable as long as it is plural.

さらに、上記第１及び第２実施形態では、色素増感太陽電池モジュールユニット１００Ａ，１００Ｂの各々において、色素増感太陽電池５０の対極２０における突出部２３の突出方向が同じとなっているが、同じである必要はなく、互いに異なるものであってもよい。   Furthermore, in the said 1st and 2nd embodiment, although the protrusion direction of the protrusion part 23 in the counter electrode 20 of the dye-sensitized solar cell 50 is the same in each of the dye-sensitized solar cell module units 100A and 100B, They need not be the same and may be different from each other.

さらに、上記第１及び第２実施形態では、ランド部１４ｃが集電配線１４に含まれており、ランド部１４ｃに突出部２３が接合されているが、ランド部１４ｃは、透明導電膜１２に設けられてもよい。またランド部１４ｃは省略可能である。   Further, in the first and second embodiments, the land portion 14 c is included in the current collector wiring 14, and the protruding portion 23 is joined to the land portion 14 c, but the land portion 14 c is connected to the transparent conductive film 12. It may be provided. Further, the land portion 14c can be omitted.

さらにまた、上記第１及び第２実施形態では、酸化物半導体層１３は、透明導電膜１２の上に設けられているが、金属基板２１の上に設けられてもよい。この場合、酸化物半導体層１３と金属基板２１とで作用極が構成され、透明基板１１と透明導電膜１２とで対極が構成される。   Furthermore, in the first and second embodiments, the oxide semiconductor layer 13 is provided on the transparent conductive film 12, but may be provided on the metal substrate 21. In this case, the oxide semiconductor layer 13 and the metal substrate 21 constitute a working electrode, and the transparent substrate 11 and the transparent conductive film 12 constitute a counter electrode.

また上記第１及び第２実施形態では、隣り合う２つの色素増感太陽電池５０のうち一方の色素増感太陽電池５０の本体部２５の縁部２５ａの一部から突出する突出部２３と、他方の色素増感太陽電池５０の集電配線１４のランド部１４ｃとが抵抗溶接により接続されているが、隣り合う２つの色素増感太陽電池５０のうち一方の色素増感太陽電池５０の本体部２５の縁部２５ａの全部から突出する突出部２３と、他方の色素増感太陽電池５０の集電配線１４のランド部１４ｃとが抵抗溶接により接続されていてもよい。   Moreover, in the said 1st and 2nd embodiment, the protrusion part 23 which protrudes from a part of edge 25a of the main-body part 25 of one dye-sensitized solar cell 50 among two adjacent dye-sensitized solar cells 50, The land portion 14c of the current collecting wiring 14 of the other dye-sensitized solar cell 50 is connected by resistance welding, but the main body of one dye-sensitized solar cell 50 of two adjacent dye-sensitized solar cells 50. The protruding portion 23 protruding from the entire edge portion 25a of the portion 25 and the land portion 14c of the current collecting wiring 14 of the other dye-sensitized solar cell 50 may be connected by resistance welding.

以下、本発明の内容を、実施例を挙げてより具体的に説明するが、本発明は下記の実施例に限定されるものではない。   Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

（実施例１）
まず表面の寸法が500ｍｍ×500ｍｍで厚さ4ｍｍのガラスからなる透明基板の表面上に、ＦＴＯからなる厚さ１μｍの透明導電膜を形成してなる透明導電性基板を用意した。そして、透明導電膜に対しエッチングによりパターニングを行った。 Example 1
First, a transparent conductive substrate was prepared by forming a 1 μm thick transparent conductive film made of FTO on the surface of a transparent substrate made of glass having a surface dimension of 500 mm × 500 mm and a thickness of 4 mm. Then, the transparent conductive film was patterned by etching.

次に、透明導電膜上に、酸化物半導体層形成用ペースト（Solaronix社製、Ｔｉ Nanoxide-T）を、スクリーン印刷機で塗布及び乾燥を３回繰り返した後、電気炉にて５００℃で１時間焼結して多孔質酸化物半導体層を形成した。   Next, an oxide semiconductor layer forming paste (manufactured by Solaronix, Ti Nanoxide-T) was repeatedly applied and dried three times with a screen printing machine on the transparent conductive film, and then 1 ° C. at 500 ° C. in an electric furnace. The porous oxide semiconductor layer was formed by time sintering.

次に、厚膜用の市販の銀ペーストを用い、上記多孔質酸化物半導体層を包囲するように透明導電膜上に塗布した後、乾燥させた。この塗布及び乾燥をスクリーン印刷機にて３回繰り返して行った。その後、銀ペーストを電気炉にて５００℃で１時間焼結した。次に、電解質が接触する領域に、配線を保護するガラスペーストを塗布した後、乾燥させた。この塗布及び乾燥を複数回繰り返し、ガラスペーストを電気炉にて１時間焼結させた。こうして作用極を得た。   Next, using a commercially available silver paste for thick film, it was applied on the transparent conductive film so as to surround the porous oxide semiconductor layer, and then dried. This application and drying were repeated three times with a screen printer. Thereafter, the silver paste was sintered in an electric furnace at 500 ° C. for 1 hour. Next, a glass paste for protecting the wiring was applied to a region where the electrolyte was in contact, and then dried. This application and drying were repeated a plurality of times, and the glass paste was sintered in an electric furnace for 1 hour. Thus, a working electrode was obtained.

そして、上記のようにして得られた作用極を、１：１（体積比）で混合したアセトニトリル及びｔｅｒｔ−ブタノールの混合溶媒を含み、ルテニウム色素（Ｎ７１９）の濃度を０．３ｍＭとした色素溶液の中に浸漬させ、その色素を多孔質半導体層に吸着させた後に上記混合溶媒で余分な色素を洗い流し、乾燥させることで、光増感色素を多孔質半導体層に吸着させた。   The working solution obtained as described above contains a mixed solvent of acetonitrile and tert-butanol mixed at 1: 1 (volume ratio), and a dye solution having a ruthenium dye (N719) concentration of 0.3 mM. Then, the dye was adsorbed on the porous semiconductor layer, and then the excess dye was washed away with the mixed solvent and dried to adsorb the photosensitizing dye to the porous semiconductor layer.

一方、対極は、以下のようにして準備した。   On the other hand, the counter electrode was prepared as follows.

即ちはじめに厚さ２００μｍのＴｉ板を用意し、このＴｉ板に、三次元ＲＦスパッタ装置を用いてＰｔを蒸着させ、対極を得た。   First, a Ti plate having a thickness of 200 μm was prepared, and Pt was vapor-deposited on the Ti plate using a three-dimensional RF sputtering apparatus to obtain a counter electrode.

次に、作用極の上に、エチレン−メタクリル酸共重合体（商品名：ニュクレル、三井・デュポンポリケミカル社製）からなる四角環状の樹脂シート（幅２ｍｍ、厚さ５０μｍ）を配置し、この樹脂シートを１５０℃で加熱溶融することにより作用極の上に固定した。   Next, a quadrangular annular resin sheet (width 2 mm, thickness 50 μm) made of an ethylene-methacrylic acid copolymer (trade name: Nucrel, manufactured by Mitsui DuPont Polychemical Co., Ltd.) is placed on the working electrode. The resin sheet was fixed on the working electrode by heating and melting at 150 ° C.

次に、作用極上であって封止部の内側に、メトキシアセトニトリルを溶媒とする揮発性電解質を注入した。   Next, a volatile electrolyte using methoxyacetonitrile as a solvent was injected on the working electrode and inside the sealing portion.

そして、対極を、触媒膜を作用極に向けた状態で封止部と重ね合わせ、対極及び作用極の周縁部を熱圧着した。こうして、色素増感太陽電池を得た。   Then, the counter electrode was overlapped with the sealing portion with the catalyst film facing the working electrode, and the peripheral portions of the counter electrode and the working electrode were thermocompression bonded. Thus, a dye-sensitized solar cell was obtained.

次に、隣り合う２つの色素増感太陽電池において、一方の色素増感太陽電池の対極のうち他方の色素増感太陽電池側の縁部と、他方の色素増感太陽電池の集電配線とを抵抗溶接により接合させた。抵抗溶接は、２つの電極をいずれもチタン箔に押し当て、抵抗溶接用電極の間に1.0kAの電流を10ミリ秒間印加した。このとき、２つの抵抗溶接用電極間の間隔は1ｍｍとした。   Next, in two adjacent dye-sensitized solar cells, the edge on the other dye-sensitized solar cell side of the counter electrode of one dye-sensitized solar cell, and the current collector wiring of the other dye-sensitized solar cell, Were joined by resistance welding. In resistance welding, the two electrodes were both pressed against the titanium foil, and a current of 1.0 kA was applied between the resistance welding electrodes for 10 milliseconds. At this time, the interval between the two resistance welding electrodes was 1 mm.

こうして、8個の色素増感太陽電池を含む１つの色素増感太陽電池モジュールユニットからなる色素増感太陽電池モジュールを得た。   Thus, a dye-sensitized solar cell module composed of one dye-sensitized solar cell module unit including eight dye-sensitized solar cells was obtained.

（比較例１）
隣り合う２つの色素増感太陽電池において、一方の色素増感太陽電池の対極の縁部と、他方の色素増感太陽電池の集電配線とを、融点220℃のはんだによって接合させたこと以外は実施例１と同様にして色素増感太陽電池モジュールを作製した。 (Comparative Example 1)
In two adjacent dye-sensitized solar cells, the edge of the counter electrode of one dye-sensitized solar cell and the current collector wiring of the other dye-sensitized solar cell are joined by solder having a melting point of 220 ° C. Prepared a dye-sensitized solar cell module in the same manner as in Example 1.

実施例１及び比較例１で得られた色素増感太陽電池モジュールについて、接続信頼性を調べた。接続信頼性は、JIS C8938 A-1に定義された温度サイクル試験を200サイクル行うことによって調べた。なお、対極と作用極の接合部における剥離の有無を評価項目とし、剥離の無い物を合格とした。   The connection reliability of the dye-sensitized solar cell modules obtained in Example 1 and Comparative Example 1 was examined. Connection reliability was examined by performing a temperature cycle test defined in JIS C8938 A-1 for 200 cycles. In addition, the presence or absence of the peeling in the junction part of a counter electrode and a working electrode was made into the evaluation item, and the thing without peeling was set as the pass.

また実施例１及び比較例１で得られた色素増感太陽電池モジュールについて、光電変換特性を評価した。光電変換特性は、エアマス（ＡＭ）が1.5の疑似太陽光により評価を行った。結果を表１に示す。なお、光電変換特性は導電性の指標となるものである。   Moreover, about the dye-sensitized solar cell module obtained in Example 1 and Comparative Example 1, the photoelectric conversion characteristic was evaluated. Photoelectric conversion characteristics were evaluated using simulated sunlight with an air mass (AM) of 1.5. The results are shown in Table 1. Note that the photoelectric conversion characteristics serve as an index of conductivity.

また実施例１及び比較例１で得られた色素増感太陽電池モジュールについて、色素の劣化について調べた。色素の劣化は、肉眼により、色素の色が接合前と接合後で変わったか否かで判断し、明らかに変色している場合には、劣化ありと判定した。

Figure 0005680996
The dye-sensitized solar cell modules obtained in Example 1 and Comparative Example 1 were examined for deterioration of the dye. The deterioration of the dye was judged by the naked eye based on whether or not the color of the dye had changed before and after bonding. When the color was clearly changed, it was determined that there was deterioration.
Figure 0005680996

表１に示すように、実施例１で得られた色素増感太陽電池モジュールは、接続信頼性および光電変換効率のいずれについても良好であったが、比較例１の色素増感太陽電池モジュールは接続信頼性の点で合格基準に達していないことが分かった。   As shown in Table 1, the dye-sensitized solar cell module obtained in Example 1 was good in both connection reliability and photoelectric conversion efficiency, but the dye-sensitized solar cell module in Comparative Example 1 was It was found that the acceptance criteria were not reached in terms of connection reliability.

以上より、本発明の色素増感太陽電池モジュールの製造方法によれば、優れた導電性及び接続信頼性を有し、光増感色素の劣化が十分に抑制された色素増感太陽電池モジュールを製造できることが確認された。   As mentioned above, according to the manufacturing method of the dye-sensitized solar cell module of this invention, it has the outstanding electroconductivity and connection reliability, and the dye-sensitized solar cell module by which deterioration of the photosensitizing dye was fully suppressed was obtained. It was confirmed that it could be manufactured.

１０…作用極
１１…透明基板
１２…透明導電膜
１３…酸化物半導体層
１４…集電配線
１４ｃ…ランド部
１５…透明導電性基板（第１電極）
２０，３２０…対極（第２電極）
２１…金属基板
２３…突出部
３０…封止部
５０，５０Ａ〜５０Ｈ…色素増感太陽電池
１００Ａ，１００Ｂ…色素増感太陽電池モジュールユニット
２００，３００…色素増感太陽電池モジュール
３３０…導電材 DESCRIPTION OF SYMBOLS 10 ... Working electrode 11 ... Transparent substrate 12 ... Transparent electrically conductive film 13 ... Oxide semiconductor layer 14 ... Current collection wiring 14c ... Land part 15 ... Transparent conductive substrate (1st electrode)
20, 320 ... Counter electrode (second electrode)
DESCRIPTION OF SYMBOLS 21 ... Metal substrate 23 ... Projection part 30 ... Sealing part 50, 50A-50H ... Dye-sensitized solar cell 100A, 100B ... Dye-sensitized solar cell module unit 200, 300 ... Dye-sensitized solar cell module 330 ... Conductive material

Claims (9)

直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、
前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを有し、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
前記接続工程において、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とを抵抗溶接により直接接続し、前記抵抗溶接を、前記集電配線の上に前記第２電極を接触させた状態で、２つの抵抗溶接用の電極を、前記第２電極の表面に当接させることによって行う色素増感太陽電池モジュールの製造方法。 In a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
Including a connecting step of electrically connecting the plurality of dye-sensitized solar cells in series and manufacturing the dye-sensitized solar cell module unit;
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
In the connecting step, the current collection in the metal substrate of the second electrode of one dye-sensitized solar cell and the first electrode of the other dye-sensitized solar cell among two adjacent dye-sensitized solar cells. A wire is directly connected to the wiring by resistance welding, and the two electrodes for resistance welding are applied to the surface of the second electrode in a state where the second electrode is in contact with the current collecting wiring. The manufacturing method of the dye-sensitized solar cell module performed by making it contact . 直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、
前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを有し、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
前記接続工程が、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板を、他方の色素増感太陽電池の前記第１電極における前記集電配線に接合されたインサート材と抵抗溶接により接続する工程を含み、
前記インサート材が前記金属基板及び前記集電配線よりも低い抵抗を有する色素増感太陽電池モジュールの製造方法。 In a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
Including a connecting step of electrically connecting the plurality of dye-sensitized solar cells in series and manufacturing the dye-sensitized solar cell module unit;
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
The connecting step, the metal substrate of the second electrode of one of the dye-sensitized solar cell of the two dye-sensitized solar cell adjacent, the current collector in the first electrode of the other of the dye-sensitized solar cell Including the step of connecting by resistance welding with the insert material joined to the wiring,
Method of manufacturing a color Motozo sensitized solar cell module wherein the insert material has a lower resistance than the metal substrate and the current collector wire. 直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールの製造方法において、
前記複数の色素増感太陽電池を直列且つ電気的に接続して前記色素増感太陽電池モジュールユニットを製造する接続工程を含み、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを有し、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
前記第２電極が、前記金属基板に対して前記第１電極と反対側に、前記金属基板よりも低い抵抗を有する導電材をさらに有し、
前記接続工程において、隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記導電材と、他方の色素増感太陽電池の前記第１電極における前記集電配線とを抵抗溶接により接続する色素増感太陽電池モジュールの製造方法。 In a method for producing a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
Including a connecting step of electrically connecting the plurality of dye-sensitized solar cells in series and manufacturing the dye-sensitized solar cell module unit;
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
The second electrode further includes a conductive material having a resistance lower than that of the metal substrate on the side opposite to the first electrode with respect to the metal substrate,
In the connecting step , the current collecting material in the second electrode of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells and the first electrode of the other dye-sensitized solar cell. method of manufacturing a color Motozo sensitized solar cell module and the wiring are connected by resistance welding. 前記接続工程において、前記抵抗溶接を3〜20ミリ秒行う、請求項１〜３のいずれか一項に記載の色素増感太陽電池モジュールの製造方法。 The method for producing a dye-sensitized solar cell module according to any one of claims 1 to 3, wherein, in the connecting step, the resistance welding is performed for 3 to 20 milliseconds. 前記第２電極の厚さが9〜200μｍである、請求項１〜４のいずれか一項に記載の色素増感太陽電池モジュールの製造方法。 The thickness of the second electrode is 9～200Myuemu, method for manufacturing a dye-sensitized solar cell module according to any one of claims 1-4. 前記集電配線の厚さが0.1〜50μｍである、請求項１〜５のいずれか一項に記載の色素増感太陽電池モジュールの製造方法。 A thickness 0.1~50μm of the current collecting wiring method for manufacturing a dye-sensitized solar cell module according to any one of claims 1-5. 直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを備え、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とが直接接続され、前記集電配線が、前記第２電極の前記金属基板よりも低い抵抗を有する金属で構成され、
前記集電配線と前記第２電極との間に、前記金属基板の金属と前記集電配線の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュール。 In a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
Of the two adjacent dye-sensitized solar cells, the metal substrate of the second electrode of one dye-sensitized solar cell is directly connected to the current collector wiring of the first electrode of the other dye-sensitized solar cell. The current collector wiring is made of a metal having a lower resistance than the metal substrate of the second electrode,
A dye-sensitized solar cell module, wherein an alloy portion made of an alloy of a metal of the metal substrate and a metal of the current collector wiring is provided between the current collector wiring and the second electrode. 直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを備え、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記金属基板と、他方の色素増感太陽電池の前記第１電極における前記集電配線とがインサート材を介して接続され、
前記金属基板と前記インサート材との間に、前記金属基板の金属と前記インサート材の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュール。 In a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
Of the two adjacent dye-sensitized solar cells, the metal substrate of the second electrode of one dye-sensitized solar cell and the current collector wiring of the first electrode of the other dye-sensitized solar cell are insert materials. Connected through
A dye-sensitized solar cell module, wherein an alloy part made of an alloy of a metal of the metal substrate and a metal of the insert material is provided between the metal substrate and the insert material. 直列且つ電気的に接続される複数の色素増感太陽電池を含む色素増感太陽電池モジュールユニットを有する色素増感太陽電池モジュールにおいて、
前記色素増感太陽電池が、
透明基板及び前記透明基板上に設けられる透明導電膜を有する第１電極と、
前記第１電極に対向し、不動態膜を有する金属からなる金属基板を含む第２電極と、
前記第１電極又は前記第２電極に設けられる酸化物半導体層と、
前記透明導電膜上に設けられる集電配線と、
前記第１電極と前記第２電極との間に設けられる電解質と、
前記第１電極及び前記第２電極を連結させる封止部とを備え、
前記複数の色素増感太陽電池における前記透明基板として１つの透明基板が共通に用いられ、
前記第２電極が、前記金属基板に対して前記第１電極と反対側に、前記金属基板よりも低い抵抗を有する導電材をさらに有し、
隣り合う２つの色素増感太陽電池のうち一方の色素増感太陽電池の前記第２電極の前記導電材と、他方の色素増感太陽電池の前記第１電極における前記集電配線とが直接接続され、
前記集電配線と前記導電材との間に、前記集電配線の金属と前記導電材の金属との合金からなる合金部が設けられている、色素増感太陽電池モジュール。
In a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of metal having a passive film facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
Current collection wiring provided on the transparent conductive film;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for connecting the first electrode and the second electrode;
One transparent substrate is commonly used as the transparent substrate in the plurality of dye-sensitized solar cells,
The second electrode further includes a conductive material having a resistance lower than that of the metal substrate on the side opposite to the first electrode with respect to the metal substrate,
Of the two adjacent dye-sensitized solar cells, the conductive material of the second electrode of one dye-sensitized solar cell is directly connected to the current collector wiring of the first electrode of the other dye-sensitized solar cell. And
A dye-sensitized solar cell module, wherein an alloy portion made of an alloy of a metal of the current collector wiring and a metal of the conductive material is provided between the current collector wiring and the conductive material.
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