JP2005294002A - Photoelectric conversion element - Google Patents

Photoelectric conversion element Download PDF

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JP2005294002A
JP2005294002A JP2004106617A JP2004106617A JP2005294002A JP 2005294002 A JP2005294002 A JP 2005294002A JP 2004106617 A JP2004106617 A JP 2004106617A JP 2004106617 A JP2004106617 A JP 2004106617A JP 2005294002 A JP2005294002 A JP 2005294002A
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housing
working electrode
main body
dye
counter electrode
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JP4606764B2 (en
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Tetsuya Ezure
哲也 江連
Nobuo Tanabe
信夫 田辺
Hiroshi Matsui
浩志 松井
Kenichi Okada
顕一 岡田
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Fujikura Ltd
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Fujikura Ltd
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Priority to PCT/JP2004/011404 priority patent/WO2005015678A1/en
Priority to KR1020067002251A priority patent/KR100847551B1/en
Priority to EP04771391A priority patent/EP1667274A4/en
Priority to US10/566,985 priority patent/US20070125420A1/en
Priority to CN 200810186129 priority patent/CN101452771B/en
Priority to CN 200810147287 priority patent/CN101355186B/en
Priority to CN 200810147288 priority patent/CN101355187B/en
Priority to AU2004302117A priority patent/AU2004302117B2/en
Priority to TW093123330A priority patent/TWI294187B/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/542Dye sensitized solar cells

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element excellent in power generation efficiency and easy to repair or replace when a fault is generated. <P>SOLUTION: A dye-sensitized solar cell 10 is equipped with a working electrode 14 in which a porous oxide semiconductor layer 13 having sensitizing dye carried on the surface is formed on one surface 14a, a counter electrode 18 positioned so as to face one surface 14a, an electrolyte layer 15 formed between the working electrode 14 and the counter electrode 18, and a housing 30 for housing them. The housing 30 is constituted of a main body 31 covering the side of a laminated body 20 and the other surface 18b of the counter electrode 18 and a cover 32 coming in contact with the other surface 14b of the working electrode 14 and fixing the laminated body 20 to the main body 31, and the cover 32 is formed with a member having an optical property transmitting sunlight and removably fixed to the main body 31. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、色素増感太陽電池などの光電変換素子に関する。   The present invention relates to a photoelectric conversion element such as a dye-sensitized solar cell.

環境問題、資源問題などを背景に、クリーンエネルギーとしての太陽電池が注目を集めている。太陽電池としては単結晶、多結晶あるいはアモルファスのシリコンを用いたものがある。しかしながら、従来のシリコン系太陽電池は、製造コストが高い上に、原料供給が不充分であるなどの課題が残されているため、普及していない。
また、Cu−In−Se系(CIS系とも呼ぶ)などの化合物系太陽電池も開発されており、この化合物系太陽電池は極めて高い光電変換効率を示すなど優れた特徴を有している。しかしながら、この化合物系太陽電池も、コストや環境負荷などの問題から普及していない。
Against the backdrop of environmental problems and resource problems, solar cells as clean energy are attracting attention. Some solar cells use single crystal, polycrystalline or amorphous silicon. However, conventional silicon-based solar cells are not widely used because of problems such as high production costs and insufficient supply of raw materials.
In addition, a compound solar cell such as a Cu-In-Se system (also referred to as a CIS system) has been developed, and this compound solar cell has excellent characteristics such as extremely high photoelectric conversion efficiency. However, this compound solar cell is not popular due to problems such as cost and environmental load.

これらの太陽電池に対して、スイスのグレッツェルらのグループなどから提案された色素増感型太陽電池は、安価で、かつ、高い光電変換効率が得られる光電変換素子として注目されている。   In contrast to these solar cells, dye-sensitized solar cells proposed by the group of Gretzel et al. In Switzerland are attracting attention as photoelectric conversion elements that are inexpensive and can provide high photoelectric conversion efficiency.

図3は、従来の色素増感型太陽電池の一例を示す概略断面図である。
この色素増感型太陽電池100は、増感色素を担持させた多孔質半導体電極(以下、「色素増感半導体電極」と言うこともある。)103が一方の面に形成された第一基板101と、導電膜104が形成された第二基板105と、これらの間に封入されたゲル状電解質などからなる電解質層106とから概略構成されている。
FIG. 3 is a schematic cross-sectional view showing an example of a conventional dye-sensitized solar cell.
This dye-sensitized solar cell 100 is a first substrate on which a porous semiconductor electrode (hereinafter also referred to as “dye-sensitized semiconductor electrode”) 103 carrying a sensitizing dye is formed on one surface. 101, a second substrate 105 on which a conductive film 104 is formed, and an electrolyte layer 106 made of a gel electrolyte or the like enclosed between them.

第一基板101としては光透過性の板材が用いられ、第一基板101の色素増感半導体電極103と接する面には導電性を付与するために透明導電膜102が設けられている。また、第一基板101、透明導電膜102および色素増感半導体電極103から作用極108が構成されている。   A light transmissive plate material is used as the first substrate 101, and a transparent conductive film 102 is provided on the surface of the first substrate 101 in contact with the dye-sensitized semiconductor electrode 103 in order to impart conductivity. The working electrode 108 is composed of the first substrate 101, the transparent conductive film 102, and the dye-sensitized semiconductor electrode 103.

一方、第二基板105としては、電解質層106と接する側の面には導電性を付与するために炭素や白金などからなる導電膜104が設けられている。また、第二基板105および導電膜104から対極109が構成されている。  On the other hand, as the second substrate 105, a conductive film 104 made of carbon, platinum, or the like is provided on the surface in contact with the electrolyte layer 106 in order to impart conductivity. Further, a counter electrode 109 is constituted by the second substrate 105 and the conductive film 104.

色素増感型太陽電池100では、色素増感半導体電極103と導電膜104が対向するように、第一基板101と第二基板105が所定の間隔をおいて配置されており、両基板間の周縁部に熱可塑性樹脂からなる封止材107が設けられている。この封止材107は、電解質層106に含まれる電解液が漏出したり、揮発性成分が揮発したりすることを防ぐ役目を果たしている。  In the dye-sensitized solar cell 100, the first substrate 101 and the second substrate 105 are arranged at a predetermined interval so that the dye-sensitized semiconductor electrode 103 and the conductive film 104 face each other. A sealing material 107 made of a thermoplastic resin is provided at the peripheral edge. The sealing material 107 serves to prevent leakage of the electrolyte contained in the electrolyte layer 106 and volatilization of volatile components.

次に、色素増感型太陽電池100の製造方法の概略を説明する。
まず、熱可塑性樹脂からなる封止材107を介して作用極108と対極109を積層した後、作用極108および対極109、または、作用極108あるいは対極109のいずれか一方を介して封止材107を加熱して、溶融することにより、作用極108と対極109を接着して、一対の電極(作用極108と対極109)からなる積層体を組み立てる。
次いで、対極109を貫通するように設けられた注入口110を通して、作用極108と対極109の間にヨウ素・ヨウ化物イオンなどの酸化・還元種を含む電解液を充填した後、注入口110を蓋111で塞ぎ、電荷移送用の電解質層106を形成し、一対の電極(作用極108と対極109)と、これらの間に挟まれた電解質層106からなる色素増感型太陽電池100を得る(例えば、特許文献1、非特許文献1参照。)。
Next, an outline of a method for manufacturing the dye-sensitized solar cell 100 will be described.
First, the working electrode 108 and the counter electrode 109 are laminated via the sealing material 107 made of thermoplastic resin, and then the sealing material is passed through the working electrode 108 and the counter electrode 109, or either the working electrode 108 or the counter electrode 109. By heating and melting 107, the working electrode 108 and the counter electrode 109 are bonded to each other to assemble a laminate including a pair of electrodes (the working electrode 108 and the counter electrode 109).
Next, an electrolytic solution containing oxidizing / reducing species such as iodine / iodide ions is filled between the working electrode 108 and the counter electrode 109 through an inlet 110 provided so as to penetrate the counter electrode 109, and then the inlet 110 is changed. A dye-sensitized solar cell 100 comprising a pair of electrodes (working electrode 108 and counter electrode 109) and an electrolyte layer 106 sandwiched between them is obtained by closing the lid 111 with a lid 111 and forming an electrolyte layer 106 for charge transfer. (For example, refer to Patent Document 1 and Non-Patent Document 1.)

上述のような色素増感型太陽電池100の製造では、積層体を組み立てる際に封止材107を溶融する熱によって、色素増感半導体電極103に担持させた増感色素が劣化するおそれがある。また、積層体を組み立てた後に、作用極108と対極109の間に電解液を充填しなければならなかった。その結果、電解液の粘度が高いと、電解液の充填には多大な時間と手間を要するという問題があった。  In the production of the dye-sensitized solar cell 100 as described above, the sensitizing dye carried on the dye-sensitized semiconductor electrode 103 may be deteriorated by heat that melts the sealing material 107 when the laminate is assembled. . In addition, after assembling the laminate, the electrolytic solution had to be filled between the working electrode 108 and the counter electrode 109. As a result, when the viscosity of the electrolytic solution is high, there is a problem that it takes a lot of time and labor to fill the electrolytic solution.

また、封止材107は熱可塑性樹脂からなるので、耐候性に劣るため、長期使用には適さないという問題があった。
さらに、作用極108と対極109の間に電解液を充填するためには、これらの電極間には所定の距離が必要である。その結果、最終的に得られる色素増感型太陽電池100の発電効率が低下するという問題があった。
特開2002−184478号公報 N.Papageorgiou et al.,J.Electrochem.Soc.,143(10),3099,1996
Further, since the sealing material 107 is made of a thermoplastic resin, it has a problem that it is not suitable for long-term use because of poor weather resistance.
Furthermore, in order to fill the electrolyte between the working electrode 108 and the counter electrode 109, a predetermined distance is required between these electrodes. As a result, there is a problem that the power generation efficiency of the dye-sensitized solar cell 100 finally obtained decreases.
JP 2002-184478 A N. Pageageriou et al. , J .; Electrochem. Soc. , 143 (10), 3099, 1996.

本発明は、前記事情に鑑みてなされたもので、安価に製造することが可能で、長期信頼性および発電効率に優れ、不具合発生時に修理や交換が容易な光電変換素子を提供することを目的とする。   The present invention has been made in view of the above circumstances, and an object thereof is to provide a photoelectric conversion element that can be manufactured at low cost, has excellent long-term reliability and power generation efficiency, and can be easily repaired or replaced when a failure occurs. And

本発明は、上記課題を解決するために、作用極、対極およびこれらの間に形成された電解質層とからなる積層体と、これらを収容する筐体とを備えた光電変換素子であって、前記筐体は、前記積層体を覆う本体と、前記積層体を前記本体に固定する蓋体とからなり、前記蓋体は前記本体に取り外し可能に固定されている光電変換素子を提供する。   In order to solve the above problems, the present invention is a photoelectric conversion element comprising a laminate composed of a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and a housing for housing them, The housing includes a main body that covers the stacked body and a lid that fixes the stacked body to the main body, and the lid provides a photoelectric conversion element that is detachably fixed to the main body.

本発明は、作用極、対極およびこれらの間に形成された電解質層とからなる積層体と、これらを収容する筐体とを備えた光電変換素子であって、前記筐体は、前記積層体を覆う本体からなり、前記作用極が前記本体に取り外し可能に固定されている光電変換素子を提供する。   The present invention is a photoelectric conversion element comprising a laminate composed of a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and a housing for housing them, the housing comprising the laminate A photoelectric conversion element comprising a main body covering the base and the working electrode being detachably fixed to the main body is provided.

上記光電変換素子において、前記対極と前記筐体との間に弾性部材が介在していることが好ましい。   In the photoelectric conversion element, an elastic member is preferably interposed between the counter electrode and the housing.

本発明の光電変換素子は、積層体を組み立てた後に、作用極と対極の間に電解液を充填する必要がないので、工程を簡略化することができる。また、本発明の光電変換素子は、熱可塑性樹脂などからなる封止材を必要としないので、耐候性すなわち長期信頼性に優れている。さらに、本発明の光電変換素子は、作用極と対極の間に距離をおく必要がないので、発電効率に優れている。  Since the photoelectric conversion element of the present invention does not need to be filled with an electrolytic solution between the working electrode and the counter electrode after the stacked body is assembled, the process can be simplified. Moreover, since the photoelectric conversion element of this invention does not require the sealing material which consists of thermoplastic resins etc., it is excellent in a weather resistance, ie, long-term reliability. Furthermore, since the photoelectric conversion element of the present invention does not require a distance between the working electrode and the counter electrode, it has excellent power generation efficiency.

また、本発明の光電変換素子は、作用極が本体の蓋を兼ねており、作用極における発電に関与する部分が蓋に覆われていないから、作用極における発電に関与する部分に入射する光量が減少することを抑制できるため、色素増感型太陽電池はより発電効率に優れたものとなる。さらに、作用極が筐体の本体に取り外し可能に固定され、作用極が本体に直接接して、積層体が本体によって封止されているから、積層体に不具合が生じた場合、これを本体から取り外して修理したり、良品に交換したりすることができる。また、本体を繰り返し使用することができるので、製造コストを削減することもできる。   In the photoelectric conversion element of the present invention, the working electrode also serves as the lid of the main body, and the portion of the working electrode that is involved in power generation is not covered by the lid. Therefore, the dye-sensitized solar cell is more excellent in power generation efficiency. Furthermore, the working electrode is detachably fixed to the main body of the housing, the working electrode is in direct contact with the main body, and the laminate is sealed by the main body. It can be removed and repaired, or replaced with a non-defective product. In addition, since the main body can be used repeatedly, the manufacturing cost can be reduced.

さらに、本発明の光電変換素子において、対極と筐体との間に弾性部材を介在させれば、積層体の積層方向に外力が加えられても、作用極と対極との間で横ズレが発生するのを抑制することができる。また、弾性部材によって、積層体を、その積層方向に柔軟性を保ちながら強固に筐体に固定することができる。   Furthermore, in the photoelectric conversion element of the present invention, if an elastic member is interposed between the counter electrode and the housing, even if an external force is applied in the stacking direction of the stacked body, there is a lateral shift between the working electrode and the counter electrode. Generation | occurrence | production can be suppressed. Further, the laminated body can be firmly fixed to the casing while maintaining flexibility in the laminating direction by the elastic member.

以下、本発明を実施した光電変換素子について、図面を参照して説明する。   Hereinafter, a photoelectric conversion element embodying the present invention will be described with reference to the drawings.

図1は、本発明に係る光電変換素子の第一の実施形態として、色素増感型太陽電池を示す概略断面図である。
図1中、符号10は色素増感型太陽電池、11は第一の基板、12は透明導電膜、13は多孔質酸化物半導体層、14は作用極、15は電解質層、16は第二の基板、17は導電膜、18は対極、19は弾性部材、20は積層体、30は筐体、31は本体、32は蓋体、41は封止部材、42は螺子をそれぞれ示している。
FIG. 1 is a schematic cross-sectional view showing a dye-sensitized solar cell as a first embodiment of a photoelectric conversion element according to the present invention.
In FIG. 1, 10 is a dye-sensitized solar cell, 11 is a first substrate, 12 is a transparent conductive film, 13 is a porous oxide semiconductor layer, 14 is a working electrode, 15 is an electrolyte layer, and 16 is a second. , 17 is a conductive film, 18 is a counter electrode, 19 is an elastic member, 20 is a laminate, 30 is a housing, 31 is a main body, 32 is a lid, 41 is a sealing member, and 42 is a screw. .

この色素増感型太陽電池10は、増感色素が表面に担持された多孔質酸化物半導体層13が一方の面14aに設けられた作用極14と、一方の面14aと対向して配置された対極18と、一方の面14aと対極18における一方の面14aと対向する面18a(以下、「対極18の一方の面18a」と称する。)との間に形成された電解質層15と、これらを収容する筐体30とから概略構成されている。   In this dye-sensitized solar cell 10, a porous oxide semiconductor layer 13 having a sensitizing dye supported on its surface is disposed opposite to a working electrode 14 provided on one surface 14a and the one surface 14a. An electrolyte layer 15 formed between the counter electrode 18 and one surface 14a and a surface 18a of the counter electrode 18 facing the one surface 14a (hereinafter referred to as "one surface 18a of the counter electrode 18"); It is schematically configured from a housing 30 that accommodates them.

なお、この色素増感太陽電池10では、電解質層15をなす電解質の大部分が、多孔質酸化物半導体層13の空隙部分に含浸された状態となっている。   In the dye-sensitized solar cell 10, most of the electrolyte forming the electrolyte layer 15 is impregnated in the void portion of the porous oxide semiconductor layer 13.

作用極14は、第一の基板11と、この一方の面11a上に順に形成された透明導電膜12および多孔質酸化物半導体層13とから構成されている。   The working electrode 14 is composed of a first substrate 11, a transparent conductive film 12 and a porous oxide semiconductor layer 13 that are sequentially formed on the one surface 11 a.

対極18は、第二の基板16と、この一方の面16a上に形成された導電膜17とから構成されている。
(導電膜17については、後述しているので、ここでは、どのようなものかの説明は不要と考えます。ここでは、色素増感太陽電池10の構成(各部材の配置、相互関係など)を説明しています。)
The counter electrode 18 includes a second substrate 16 and a conductive film 17 formed on the one surface 16a.
(Since the conductive film 17 is described later, it is not necessary to explain what it is here. Here, the configuration of the dye-sensitized solar cell 10 (arrangement of each member, mutual relationship, etc.) Is explained.)

色素増感型太陽電池10において、電解質層15を作用極14と対極18で挟んでなる積層体20が光電変換素子として機能する。   In the dye-sensitized solar cell 10, a laminate 20 in which the electrolyte layer 15 is sandwiched between the working electrode 14 and the counter electrode 18 functions as a photoelectric conversion element.

色素増感型太陽電池10において、積層体20は、積層体20の側面20aおよび対極18における他方の面18bを覆う断面凹状の本体31と、作用極14の他方の面14bに接して積層体20を本体31に固定する蓋体32とからなる筐体30内に収容されている。さらに、本体31は、弾性部材19を介して対極18の他方の面18bに接している。
また、蓋体32は、封止部材41を介して本体31に接している。さらに、蓋体32は、螺子42によって本体31に固定されている。
In the dye-sensitized solar cell 10, the stacked body 20 is in contact with the concave body body 31 covering the side surface 20 a of the stacked body 20 and the other surface 18 b of the counter electrode 18, and the other surface 14 b of the working electrode 14. It is accommodated in a housing 30 comprising a lid 32 for fixing 20 to the main body 31. Further, the main body 31 is in contact with the other surface 18 b of the counter electrode 18 through the elastic member 19.
The lid 32 is in contact with the main body 31 through the sealing member 41. Further, the lid body 32 is fixed to the main body 31 by screws 42.

なお、筐体30による積層体20の封止を十分なものとするためには、封止部材41を嵌合するための溝などからなる嵌合部(図示略)を、本体31の蓋体32と接する面31aおよび蓋体32の一方の面32aに設けることが好ましい。   In order to sufficiently seal the stacked body 20 with the housing 30, a fitting portion (not shown) including a groove for fitting the sealing member 41 is used as a lid of the main body 31. It is preferable to provide the surface 31 a in contact with 32 and one surface 32 a of the lid 32.

このような構成とすることにより、積層体20は、その上下面が本体31と蓋体32で挟み込まれて、その積層方向に押圧された状態で、筐体30内に収容される。また、この状態で、積層体20の側面20aの全域が本体31に覆われて、積層体20は筐体30によって一括して封止されている。   By setting it as such a structure, the laminated body 20 is accommodated in the housing | casing 30 in the state by which the upper and lower surfaces were pinched | interposed by the main body 31 and the cover body 32, and was pressed in the lamination direction. In this state, the entire side surface 20 a of the stacked body 20 is covered with the main body 31, and the stacked body 20 is collectively sealed by the housing 30.

第一の基板11としては、光透過性の素材からなる基板が用いられ、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリエーテルスルホンなど、通常、太陽電池の透明基板として用いられるものであればいかなるものもでも用いることができる。第一の基板11は、これらの中から電解液への耐性などを考慮して適宜選択されるが、用途上、できる限り光透過性に優れる基板が好ましい。  As the first substrate 11, a substrate made of a light-transmitting material is used, and glass, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, etc., which are usually used as transparent substrates for solar cells. Anything can be used. The first substrate 11 is appropriately selected from these in consideration of resistance to the electrolytic solution and the like, and a substrate that is as excellent in light transmittance as possible is preferable.

透明導電膜12は、第一の基板11に導電性を付与するために、その一方の面11aに形成された金属、炭素、導電性金属酸化物などからなる薄膜である。
透明導電膜12として金属薄膜や炭素薄膜を形成する場合、第一の基板11の透明性を著しく損なわない構造とする。透明導電膜12を形成する導電性金属酸化物としては、例えば、インジウム−スズ酸化物(Indium−Tin Oxide、ITO)、酸化スズ(SnO)、フッ素ドープの酸化スズなどが用いられる。
The transparent conductive film 12 is a thin film made of metal, carbon, conductive metal oxide, or the like formed on one surface 11a in order to impart conductivity to the first substrate 11.
In the case where a metal thin film or a carbon thin film is formed as the transparent conductive film 12, a structure that does not significantly impair the transparency of the first substrate 11 is adopted. Examples of the conductive metal oxide that forms the transparent conductive film 12 include indium-tin oxide (ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide.

多孔質酸化物半導体層13は、透明導電膜12の上に設けられており、その表面には増感色素が担持されている。多孔質酸化物半導体層13を形成する半導体としては特に限定されず、通常、太陽電池用の多孔質半導体を形成するのに用いられるものであればいかなるものでも用いることができる。このような半導体としては、例えば、酸化チタン(TiO)、酸化スズ(SnO)、酸化タングステン(WO)、酸化亜鉛(ZnO)、酸化ニオブ(Nb)などを用いることができる。
多孔質酸化物半導体層13を形成する方法としては、例えば、ゾルゲル法からの膜形成、微粒子の泳動電着、発泡剤による多孔質化、ポリマービーズなどとの混合物塗布後における余剰成分の除去などの方法が挙げられるが、これらに限定されるものではない。
The porous oxide semiconductor layer 13 is provided on the transparent conductive film 12, and a sensitizing dye is supported on the surface thereof. The semiconductor that forms the porous oxide semiconductor layer 13 is not particularly limited, and any semiconductor that can be used to form a porous semiconductor for solar cells can be used. As such a semiconductor, for example, titanium oxide (TiO 2 ), tin oxide (SnO 2 ), tungsten oxide (WO 3 ), zinc oxide (ZnO), niobium oxide (Nb 2 O 5 ), or the like can be used. .
Examples of the method for forming the porous oxide semiconductor layer 13 include film formation from a sol-gel method, electrophoretic electrodeposition of fine particles, porous formation with a foaming agent, removal of excess components after application of a mixture with polymer beads, and the like. However, it is not limited to these methods.

増感色素としては、ビピリジン構造、ターピリジン構造などを配位子に含むルテニウム錯体、ポルフィリン、フタロシアニンなどの含金属錯体、エオシン、ローダミン、メロシアニンなどの有機色素などを適用することができ、これらの中から、用途、使用半導体に適した励起挙動を示すものを特に限定無く選ぶことができる。  As the sensitizing dye, a ruthenium complex containing a bipyridine structure or a terpyridine structure as a ligand, a metal-containing complex such as porphyrin or phthalocyanine, or an organic dye such as eosin, rhodamine or merocyanine can be applied. Therefore, those exhibiting excitation behavior suitable for the application and the semiconductor used can be selected without particular limitation.

電解質層15は、多孔質酸化物半導体層13内に電解液を含浸させてなるものか、または、多孔質酸化物半導体層13内に電解液を含浸させた後に、この電解液を適当なゲル化剤を用いてゲル化(擬固体化)して、多孔質酸化物半導体層13と一体に形成されてなるものが用いられる。  The electrolyte layer 15 is formed by impregnating a porous oxide semiconductor layer 13 with an electrolytic solution, or after impregnating the porous oxide semiconductor layer 13 with an electrolytic solution, the electrolytic solution is applied to an appropriate gel. A material formed by gelation (pseudo-solidification) using an agent and integrally formed with the porous oxide semiconductor layer 13 is used.

電解液としては、ヨウ素、ヨウ化物イオン、ターシャリーブチルピリジンなどの電解質成分が、エチレンカーボネートやメトキシアセトニトリルなどの有機溶媒に溶解されてなるものが用いられる。  As the electrolytic solution, an electrolytic solution in which an electrolyte component such as iodine, iodide ion, or tertiary butyl pyridine is dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile is used.

電解液をゲル化する際に用いられるゲル化剤としては、ポリフッ化ビニリデン、ポリエチレンオキシド誘導体、アミノ酸誘導体などが挙げられる。  Examples of the gelling agent used when gelling the electrolytic solution include polyvinylidene fluoride, polyethylene oxide derivatives, amino acid derivatives, and the like.

第二の基板16としては、第一の基板11と同様のものや、特に光透過性をもつ必要がないことから金属板、合成樹脂板などが用いられる。  As the second substrate 16, a metal plate, a synthetic resin plate, or the like is used because it is not necessary to have the same light transmission as the first substrate 11.

導電膜17は、第二の基板16に導電性を付与するために、その一方の面16aに形成された白金などの金属、炭素などからなる薄膜である。導電膜17としては、例えば炭素や白金などの層を、蒸着、スパッタ、塩化白金酸塗布後に熱処理を行ったものが好適に用いられるが、電極として機能するものであれば特に限定されるものではない。  The conductive film 17 is a thin film made of a metal such as platinum, carbon, or the like formed on one surface 16a of the second substrate 16 in order to impart conductivity. As the conductive film 17, for example, a layer of carbon, platinum, or the like, which has been heat-treated after vapor deposition, sputtering, and application of chloroplatinic acid is preferably used, but is not particularly limited as long as it functions as an electrode. Absent.

弾性部材19としては、発泡ポリエチレン、発泡ポリウレタン、ゴムスポンジなどが用いられる。
色素増感型太陽電池10では、積層体20を筐体30によって封止することにより、積層体20にはその積層方向に外力が加えられる。弾性部材19を対極18と本体31との間に介在させることにより、この外力によって、作用極14と対極18との間で横ズレが発生するのを抑制することができる。また、弾性部材19によって、積層体20を、その積層方向に柔軟性を保ちながら強固に筐体30に固定することができる。
As the elastic member 19, foamed polyethylene, foamed polyurethane, rubber sponge, or the like is used.
In the dye-sensitized solar cell 10, an external force is applied to the stacked body 20 in the stacking direction by sealing the stacked body 20 with the housing 30. By interposing the elastic member 19 between the counter electrode 18 and the main body 31, it is possible to suppress the occurrence of lateral deviation between the working electrode 14 and the counter electrode 18 due to this external force. In addition, the laminate 20 can be firmly fixed to the housing 30 by the elastic member 19 while maintaining flexibility in the stacking direction.

本体31を形成する素材としては特に限定されないが、各種金属、セラミックス、各種合成樹脂などが用いられる。  Although it does not specifically limit as a raw material which forms the main body 31, Various metals, ceramics, various synthetic resins, etc. are used.

蓋体32としては、太陽光を透過する光学特性を有する部材が用いられる。太陽光を透過する光学特性を有する部材としては特に限定されないが、例えば、アクリル、ポリカーボネート、ポリ塩化ビニル、ソーダガラスなど透明で剛性のある材質からなる部材が挙げられる。   As the lid body 32, a member having optical characteristics that transmits sunlight is used. Although it does not specifically limit as a member which has the optical characteristic which permeate | transmits sunlight, For example, the member which consists of a transparent and rigid material, such as an acryl, a polycarbonate, a polyvinyl chloride, soda glass, is mentioned.

封止部材41としては、ニトリルゴム、シリコンゴム、ウレタンゴム、フッ素ゴムなどの弾性材料や、ポリ四フッ化エチレンなどからなるOリング、ガスケットなどが用いられる。   As the sealing member 41, an elastic material such as nitrile rubber, silicon rubber, urethane rubber, or fluorine rubber, an O-ring made of polytetrafluoroethylene, a gasket, or the like is used.

螺子42としては、蓋体32を本体31に接合、固定することができるものであればいかなるものでも用いることができる。   Any screw 42 can be used as long as it can join and fix the lid 32 to the main body 31.

なお、この実施形態では、蓋体32を本体31に接合、固定する手段として、螺子42を例示したが、本発明の光電変換素子はこれに限定されない。本発明の光電変換素子にあっては、蓋体を枠体に接合、固定する手段としては、例えば、枠体に設けられた被係止部に、蓋体に回転可能に設けられたフラップ状の係止部を係止する手段や、枠体の枠部、押圧部および蓋体の表面に接するように筐体の外側に装着される、断面コ字形スリーブ状のバネのクランプ力によって挟み込む手段などを用いることもできる。また、前記被係止部に係止部を係止する手段は、被嵌合部に嵌合部を嵌合する手段であってもよい。   In this embodiment, the screw 42 is exemplified as means for joining and fixing the lid 32 to the main body 31, but the photoelectric conversion element of the present invention is not limited to this. In the photoelectric conversion element of the present invention, as a means for joining and fixing the lid body to the frame body, for example, a flap shape provided rotatably on the lid body at a locked portion provided in the frame body Means for locking the locking part of the frame, and means for clamping by the clamping force of a spring having a U-shaped cross-section sleeve mounted on the outside of the housing so as to contact the surface of the frame part, the pressing part and the lid of the frame Etc. can also be used. The means for locking the locking portion to the locked portion may be a means for fitting the fitting portion to the fitting portion.

以上説明したように、色素増感型太陽電池10では、積層体20を組み立てた後に、作用極14と対極18の間に電解液を充填する必要がないので、工程を簡略化することができる。また、色素増感型太陽電池10は、熱可塑性樹脂などからなる封止材を必要としないので、耐候性すなわち長期信頼性に優れている。さらに、色素増感型太陽電池10は、作用極14と対極18の間に距離をおく必要がないので、発電効率に優れている。
また、色素増感型太陽電池10では、蓋体32が封止部材41を介して本体31に取り外し可能に固定されて、積層体20が筐体30によって封止されているから、積層体20に不具合が生じた場合、これを筐体30から取り外して修理したり、良品に交換したりすることができる。また、筐体30を繰り返し使用することができるので、製造コストを削減することもできる。
As described above, in the dye-sensitized solar cell 10, it is not necessary to fill the electrolyte solution between the working electrode 14 and the counter electrode 18 after the stacked body 20 is assembled, so that the process can be simplified. . Moreover, since the dye-sensitized solar cell 10 does not require a sealing material made of a thermoplastic resin or the like, it has excellent weather resistance, that is, long-term reliability. Furthermore, the dye-sensitized solar cell 10 is excellent in power generation efficiency because it is not necessary to provide a distance between the working electrode 14 and the counter electrode 18.
In the dye-sensitized solar cell 10, the lid body 32 is detachably fixed to the main body 31 via the sealing member 41, and the laminated body 20 is sealed by the housing 30. If a problem occurs, it can be removed from the housing 30 for repair or replaced with a non-defective product. Moreover, since the housing | casing 30 can be used repeatedly, manufacturing cost can also be reduced.

次に、本発明に係る光電変換素子の製造方法の一実施形態を、図1を参照して説明する。
この実施形態では、まず、第一の基板11における一方の面11a上に透明導電膜12および多孔質酸化物半導体層13が所定の方法により順に形成されてなる作用極14を用意する。
Next, an embodiment of a method for producing a photoelectric conversion element according to the present invention will be described with reference to FIG.
In this embodiment, first, a working electrode 14 is prepared in which a transparent conductive film 12 and a porous oxide semiconductor layer 13 are sequentially formed on one surface 11a of the first substrate 11 by a predetermined method.

次いで、多孔質酸化物半導体層13に、予めゲル化剤が添加された電解液を滴下して含浸させた後、この電解液をゲル化させて、多孔質酸化物半導体層13と一体をなす電解質層15を形成する。   Next, the porous oxide semiconductor layer 13 is dropped and impregnated with an electrolytic solution to which a gelling agent has been added in advance, and then the electrolytic solution is gelled so as to be integrated with the porous oxide semiconductor layer 13. The electrolyte layer 15 is formed.

次いで、対極18の他方の面18bが、弾性部材19を介して本体31の内側の底面31aに接するように、本体31内に作用極14を配置する。   Next, the working electrode 14 is disposed in the main body 31 so that the other surface 18 b of the counter electrode 18 contacts the bottom surface 31 a inside the main body 31 via the elastic member 19.

次いで、導電膜17が電解質層15に重なるように、対極18を作用極13に重ねて、電解質層15を作用極14と対極18で挟んでなる積層体20を、本体31内に形成する。   Next, a laminate 20 is formed in the main body 31 such that the counter electrode 18 is stacked on the working electrode 13 so that the conductive film 17 overlaps the electrolyte layer 15, and the electrolyte layer 15 is sandwiched between the working electrode 14 and the counter electrode 18.

次いで、作用極14の他方の面14bを覆うように蓋体32を配する。   Next, the lid body 32 is disposed so as to cover the other surface 14 b of the working electrode 14.

次いで、蓋体32の外側から積層体20の積層方向に荷重を加えながら、蓋体32を、封止部材41を介して本体31に螺子42で固定し、筐体30で積層体20を封止することにより、色素増感型太陽電池10を得る。   Next, while applying a load from the outside of the lid 32 in the laminating direction of the laminate 20, the lid 32 is fixed to the main body 31 with the screw 42 via the sealing member 41, and the laminate 20 is sealed with the casing 30. By stopping, the dye-sensitized solar cell 10 is obtained.

図2は、本発明に係る光電変換素子の第二の実施形態として、色素増感型太陽電池を示す概略断面図である。
図2中、符号50は色素増感型太陽電池、51は第一の基板、52は透明導電膜、53は多孔質酸化物半導体層、54は作用極、55は電解質層、56は第二の基板、57は導電膜、58は対極、59は弾性部材、60は積層体、70は筐体(「本体」と言うこともある。)、81は封止部材、82は螺子をそれぞれ示している。
FIG. 2 is a schematic cross-sectional view showing a dye-sensitized solar cell as a second embodiment of the photoelectric conversion element according to the present invention.
In FIG. 2, 50 is a dye-sensitized solar cell, 51 is a first substrate, 52 is a transparent conductive film, 53 is a porous oxide semiconductor layer, 54 is a working electrode, 55 is an electrolyte layer, and 56 is a second. , 57 is a conductive film, 58 is a counter electrode, 59 is an elastic member, 60 is a laminate, 70 is a housing (sometimes referred to as a “main body”), 81 is a sealing member, and 82 is a screw. ing.

この色素増感型太陽電池50は、増感色素が表面に担持された多孔質酸化物半導体層53が一方の面54aに設けられた作用極54と、一方の面54aと対向して配置された対極58と、一方の面54aと対極58におけるこの面と対向する面(以下、「一方の面」と称する。)58aとの間に形成された電解質層55と、これらを収容する筐体70とから概略構成されている。   In this dye-sensitized solar cell 50, a porous oxide semiconductor layer 53 having a sensitizing dye supported on the surface thereof is disposed opposite to the working electrode 54 provided on one surface 54a and the one surface 54a. An electrolyte layer 55 formed between the counter electrode 58, one surface 54 a and a surface (hereinafter referred to as “one surface”) 58 a of the counter electrode 58 facing the surface, and a housing for housing these layers. 70.

なお、この色素増感太陽電池50では、電解質層55は多孔質酸化物半導体層53と一体に形成されている。   In the dye-sensitized solar cell 50, the electrolyte layer 55 is formed integrally with the porous oxide semiconductor layer 53.

作用極54は、第一の基板51と、この一方の面51a上に順に形成された透明導電膜52および多孔質酸化物半導体層53とから構成されている。また、作用極54の周縁部54cには、多孔質酸化物半導体層53が設けられておらず、第一の基板51と透明導電膜52で構成されている。   The working electrode 54 includes a first substrate 51, and a transparent conductive film 52 and a porous oxide semiconductor layer 53 that are sequentially formed on the one surface 51a. Further, the peripheral edge 54 c of the working electrode 54 is not provided with the porous oxide semiconductor layer 53, and is composed of the first substrate 51 and the transparent conductive film 52.

対極58は、第二の基板56と、この一方の面56a上に形成された導電膜57とから構成されている。   The counter electrode 58 includes a second substrate 56 and a conductive film 57 formed on the one surface 56a.

色素増感型太陽電池50において、電解質層55を作用極54と対極58で挟んでなる積層体60が光電変換素子として機能する。   In the dye-sensitized solar cell 50, a laminate 60 in which the electrolyte layer 55 is sandwiched between the working electrode 54 and the counter electrode 58 functions as a photoelectric conversion element.

色素増感型太陽電池50において、積層体60は、積層体60の側面60aおよび対極58における他方の面58bを覆う断面凹状の本体70内に収容されている。さらに、本体70は、弾性部材59を介して対極58の他方の面58bに接している。   In the dye-sensitized solar cell 50, the stacked body 60 is housed in a body 70 having a concave cross section that covers the side surface 60 a of the stacked body 60 and the other surface 58 b of the counter electrode 58. Further, the main body 70 is in contact with the other surface 58 b of the counter electrode 58 via the elastic member 59.

また、作用極54の周縁部54cは、封止部材81を介して本体70に直接、接している。さらに、作用極54の周縁部54cは、螺子82によって本体70に固定されている。
なお、本体70による積層体60の封止を十分なものとするためには、封止部材81を嵌合するための溝などからなる嵌合部(図示略)を、本体70の周縁部54cと接する面70aおよび周縁部54cの本体70と接する面54dに設けることが好ましい。
Further, the peripheral edge 54 c of the working electrode 54 is in direct contact with the main body 70 via the sealing member 81. Further, the peripheral edge 54 c of the working electrode 54 is fixed to the main body 70 by a screw 82.
In order to sufficiently seal the laminate 60 with the main body 70, a fitting portion (not shown) including a groove for fitting the sealing member 81 is used as the peripheral portion 54 c of the main body 70. It is preferable to provide the surface 70a in contact with the body 70 and the surface 54d in contact with the main body 70 of the peripheral edge 54c.

このような構成とすることにより、積層体60の側面60aの全域が筐体70に覆われて、その積層方向に押圧された状態で、積層体60は筐体70によって一括して封止される。   With such a configuration, the entire surface of the side surface 60a of the laminate 60 is covered with the casing 70, and the laminate 60 is collectively sealed by the casing 70 while being pressed in the stacking direction. The

第一の基板51としては、上記第一の基板11と同様のものが用いられる。
透明導電膜52としては、上記透明導電膜12と同様のものが設けられる。
多孔質酸化物半導体層53を形成する半導体としては、上記多孔質酸化物半導体層13を形成する半導体と同様のものが用いられる。
As the first substrate 51, the same substrate as the first substrate 11 is used.
As the transparent conductive film 52, the same thing as the said transparent conductive film 12 is provided.
As a semiconductor for forming the porous oxide semiconductor layer 53, the same semiconductor as that for forming the porous oxide semiconductor layer 13 is used.

増感色素としては、上述の第一の実施形態と同様のものが用いられる。
電解質層55としては、上記電解質層15と同様のものが設けられる。
電解液としては、上述の第一の実施形態と同様のものが用いられる。
ゲル化剤としては、上述の第一の実施形態と同様のものが用いられる。
As the sensitizing dye, those similar to those in the first embodiment described above are used.
As the electrolyte layer 55, the same one as the electrolyte layer 15 is provided.
As the electrolytic solution, the same one as in the first embodiment described above is used.
As the gelling agent, those similar to those in the first embodiment described above are used.

第二の基板56としては、上記第二の基板16と同様のものが用いられる。
導電膜57としては、上記導電膜17と同様のものが設けられる。
弾性部材59としては、上記弾性部材19と同様のものが用いられる。
As the second substrate 56, the same substrate as the second substrate 16 is used.
The conductive film 57 is the same as the conductive film 17.
As the elastic member 59, the same one as the elastic member 19 is used.

筐体70を形成する素材としては特に限定されないが、上記本体31を形成する素材と同様のものが用いられる。
封止部材81としては、上記封止部材41と同様のものが用いられる。
螺子82としては、上記螺子42と同様のものが用いられる。
The material forming the housing 70 is not particularly limited, but the same material as that forming the main body 31 is used.
As the sealing member 81, the same member as the sealing member 41 is used.
As the screw 82, the same one as the screw 42 is used.

なお、この実施形態では、作用極54を筐体70に接合、固定する手段として、螺子82を例示したが、本発明の光電変換素子はこれに限定されない。本発明の光電変換素子にあっては、蓋体を枠体に接合、固定する手段としては、例えば、筐体に設けられた被係止部に、作用極に回転可能に設けられたフラップ状の係止部を係止する手段や、作用極および筐体の表面に接するようにこれらの外側に装着される、断面コ字形スリーブ状のバネのクランプ力によって挟み込む手段などを用いることもできる。また、前記被係止部に係止部を係止する手段は、被嵌合部に嵌合部を嵌合する手段であってもよい。   In this embodiment, the screw 82 is exemplified as means for joining and fixing the working electrode 54 to the housing 70, but the photoelectric conversion element of the present invention is not limited to this. In the photoelectric conversion element of the present invention, as means for joining and fixing the lid body to the frame body, for example, a flap-like shape provided rotatably on the working electrode at a locked portion provided in the housing There may be used means for locking the locking portion, means for clamping by the clamping force of a spring having a U-shaped cross-section sleeve attached to the outside of the working electrode and the surface of the housing. The means for locking the locking portion to the locked portion may be a means for fitting the fitting portion to the fitting portion.

以上説明したように、色素増感型太陽電池50では、積層体60を組み立てた後に、作用極54と対極58の間に電解液を充填する必要がないので、工程を簡略化することができる。また、色素増感型太陽電池50は、熱可塑性樹脂などからなる封止材を必要としないので、耐候性すなわち長期信頼性に優れている。さらに、色素増感型太陽電池50は、作用極54と対極58の間に距離をおく必要がないので、発電効率に優れている。
また、作用極54が筐体70の蓋を兼ねており、作用極54における発電に関与する部分が蓋に覆われていないから、作用極54における発電に関与する部分に入射する光量が減少することを抑制できるため、色素増感型太陽電池50はより発電効率に優れたものとなる。
また、色素増感型太陽電池50では、作用極54が封止部材81を介して筐体70に取り外し可能に固定され、作用極54が筐体70に直接、接して、積層体60が筐体70によって封止されているから、積層体60に不具合が生じた場合、これを筐体70から取り外して修理したり、良品に交換したりすることができる。また、筐体70を繰り返し使用することができるので、製造コストを削減することもできる。
As described above, in the dye-sensitized solar cell 50, it is not necessary to fill the electrolyte solution between the working electrode 54 and the counter electrode 58 after the stacked body 60 is assembled, so that the process can be simplified. . Further, since the dye-sensitized solar cell 50 does not require a sealing material made of a thermoplastic resin or the like, it has excellent weather resistance, that is, long-term reliability. Furthermore, the dye-sensitized solar cell 50 is excellent in power generation efficiency because it is not necessary to provide a distance between the working electrode 54 and the counter electrode 58.
In addition, since the working electrode 54 also serves as the lid of the housing 70 and the portion of the working electrode 54 involved in power generation is not covered with the lid, the amount of light incident on the portion of the working electrode 54 involved in power generation is reduced. Therefore, the dye-sensitized solar cell 50 is more excellent in power generation efficiency.
In the dye-sensitized solar cell 50, the working electrode 54 is detachably fixed to the housing 70 via the sealing member 81, the working electrode 54 is in direct contact with the housing 70, and the laminate 60 is housed in the housing. Since it is sealed by the body 70, when a defect occurs in the laminated body 60, it can be repaired by removing it from the housing 70 or replaced with a non-defective product. Moreover, since the housing | casing 70 can be used repeatedly, manufacturing cost can also be reduced.

本発明によれば、高粘度もしくはゲル状の電解質を容易に充填できる利点を保ちながら、発生した電子を効率良く収集することができる色素増感型太陽電池を実現することができる。また、セルに入射する光量を減少することなく、筐体との分離性も高いことから、保守性やリサイクル性も高く、環境負荷の低い太陽電池を実現することができる。   According to the present invention, it is possible to realize a dye-sensitized solar cell that can efficiently collect generated electrons while maintaining the advantage of easily filling a high-viscosity or gel electrolyte. Further, since the separation from the housing is high without reducing the amount of light incident on the cell, a solar cell with high maintainability and recyclability and low environmental load can be realized.

本発明に係る光電変換素子の第一の実施形態として、色素増感型太陽電池を示す概略断面図である。It is a schematic sectional drawing which shows a dye-sensitized solar cell as 1st embodiment of the photoelectric conversion element which concerns on this invention. 本発明に係る光電変換素子の第二の実施形態として、色素増感型太陽電池を示す概略断面図である。It is a schematic sectional drawing which shows a dye-sensitized solar cell as 2nd embodiment of the photoelectric conversion element which concerns on this invention. 従来の色素増感型太陽電池の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the conventional dye-sensitized solar cell.

符号の説明Explanation of symbols

10,50・・・色素増感型太陽電池、11,51・・・第一の基板、12,52・・・透明導電膜、13,53・・・多孔質酸化物半導体層、14,54・・・作用極、15,55・・・電解質層、16,56・・・第二の基板、17,57・・・透明導電膜、18,58・・・対極、19,59・・・弾性部材、20,60・・・積層体、30,70・・・筐体、31・・・本体、32・・・蓋体、41,81・・・封止部材、42,82・・・螺子。
DESCRIPTION OF SYMBOLS 10,50 ... Dye-sensitized solar cell 11,51 ... 1st board | substrate, 12,52 ... Transparent electrically conductive film, 13,53 ... Porous oxide semiconductor layer, 14,54 ... Working electrode, 15, 55 ... Electrolyte layer, 16, 56 ... Second substrate, 17, 57 ... Transparent conductive film, 18, 58 ... Counter electrode, 19, 59 ... Elastic member 20, 60 ... Laminated body, 30, 70 ... Housing, 31 ... Main body, 32 ... Cover, 41, 81 ... Sealing member, 42, 82 ... Screw.

Claims (3)

作用極、対極およびこれらの間に形成された電解質層とからなる積層体と、これらを収容する筐体とを備えた光電変換素子であって、
前記筐体は、前記積層体を覆う本体と、前記積層体を前記本体に固定する蓋体とからなり、前記蓋体は前記本体に取り外し可能に固定されていることを特徴とする光電変換素子。
A photoelectric conversion element comprising a laminate composed of a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and a housing for housing them,
The housing includes a main body that covers the laminated body and a lid that fixes the laminated body to the main body, and the lid is detachably fixed to the main body. .
作用極、対極およびこれらの間に形成された電解質層とからなる積層体と、これらを収容する筐体とを備えた光電変換素子であって、
前記筐体は、前記積層体を覆う本体からなり、前記作用極が前記本体に取り外し可能に固定されていることを特徴とする光電変換素子。
A photoelectric conversion element comprising a laminate composed of a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and a housing for housing them,
The housing includes a main body that covers the stacked body, and the working electrode is detachably fixed to the main body.
前記対極と前記筐体との間に弾性部材が介在していることを特徴とする請求項1または2に記載の光電変換素子。

The photoelectric conversion element according to claim 1, wherein an elastic member is interposed between the counter electrode and the housing.

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EP04771391A EP1667274A4 (en) 2003-08-06 2004-08-03 Photoelectric converter and method for manufacturing same
US10/566,985 US20070125420A1 (en) 2003-08-06 2004-08-03 Photoelectric converter and method for manufacturing same
CN 200810186129 CN101452771B (en) 2003-08-06 2004-08-03 method for manufacturing photoelectric converter
CN 200810147287 CN101355186B (en) 2003-08-06 2004-08-03 Photoelectric converter
PCT/JP2004/011404 WO2005015678A1 (en) 2003-08-06 2004-08-03 Photoelectric converter and method for manufacturing same
KR1020067002251A KR100847551B1 (en) 2003-08-06 2004-08-03 Photoelectric converter and method for manufacturing same
CN 200810147288 CN101355187B (en) 2003-08-06 2004-08-03 Photoelectric converter
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WO2009144899A1 (en) * 2008-05-27 2009-12-03 株式会社フジクラ Photoelectric conversion element

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JP2007194039A (en) * 2006-01-18 2007-08-02 Sharp Corp Dye-sensitized solar cell and module thereof
US10366842B2 (en) 2006-01-18 2019-07-30 Sharp Kabushiki Kaisha Dye-sensitized solar cell and method for manufacturing thereof
WO2009144899A1 (en) * 2008-05-27 2009-12-03 株式会社フジクラ Photoelectric conversion element
JPWO2009144899A1 (en) * 2008-05-27 2011-10-06 株式会社フジクラ Photoelectric conversion element
JP5296785B2 (en) * 2008-05-27 2013-09-25 株式会社フジクラ Photoelectric conversion element

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