WO2011111592A1 - Pigment-sensitized photovoltaic cell - Google Patents

Pigment-sensitized photovoltaic cell Download PDF

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Publication number
WO2011111592A1
WO2011111592A1 PCT/JP2011/054867 JP2011054867W WO2011111592A1 WO 2011111592 A1 WO2011111592 A1 WO 2011111592A1 JP 2011054867 W JP2011054867 W JP 2011054867W WO 2011111592 A1 WO2011111592 A1 WO 2011111592A1
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Prior art keywords
dye
electrode
solar cell
insulator
photoelectrode
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PCT/JP2011/054867
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French (fr)
Japanese (ja)
Inventor
中村　雅規
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ウシオ電機株式会社
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Priority to JP2011518630A priority Critical patent/JP4798318B1/en
Publication of WO2011111592A1 publication Critical patent/WO2011111592A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2086—Photoelectrochemical cells in the form of a fiber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a dye-sensitized solar cell.
  • it is related with the dye-sensitized solar cell which has a translucent tubular container.
  • solar cells have been developed as a new energy source with little influence on the global environment.
  • solar cells using silicon semiconductors have high conversion efficiency and excellent light stability, and are widely spread.
  • high-temperature and high-vacuum conditions are required for production, and there is a problem that the area is not easily increased and the production cost is high.
  • a photoelectrode made of a porous semiconductor filled with an electrolytic solution and adsorbed with a dye inside a transparent container and a counter electrode are provided, and the dye irradiated with sunlight emits electrons to generate electric energy.
  • a dye-sensitized solar cell that can take out the water (Patent Document 1). This type of solar cell does not require a high-vacuum chamber or the like for manufacturing, and has the advantage that it can be manufactured inexpensively with less burden on the equipment.
  • FIG. 5 (a) is a cross-sectional view of the dye-sensitized solar cell disclosed in Patent Document 1 cut in the tube axis direction
  • FIG. 5 (b) is a cross-sectional view taken along the line ZZ ′ of FIG. 5 (a). It is.
  • the solar cell 100 is provided with a transparent conductive layer 102, a dye-sensitized porous semiconductor layer 103 on which a dye is adsorbed, and an electrolyte layer 104 in this order on the inner surface of a tube 101 made of a transparent material.
  • a counter electrode 105 is inserted into the tube 101 along the tube axis. One end 105 b of the counter electrode 105 protrudes outward from the tube 101.
  • a sealing member 106 made of epoxy resin, It is insulated and sealed so that the electrolyte solution in the electrolyte layer 104 does not leak out of the tube 101.
  • Lead wires 107 and 108 are connected to the counter electrode 105 and the transparent conductive layer 102, respectively.
  • the solar cell 100 When the solar cell 100 is irradiated with sunlight, the sunlight passes through the tube 101 and the transparent conductive layer 102 and reaches the dye-sensitized porous semiconductor layer 103, where a photochemical reaction occurs and the dye emits electrons.
  • the electromotive force is generated between the lead wires 107 and 108.
  • the container since the container is circular, the change in the amount of power generation with respect to the incident angle of light can be greatly reduced.
  • a resin such as epoxy is used as the sealing member 106 that seals both ends of the tube 101.
  • the epoxy resin used for the sealing member 106 has a problem that it cannot be used for a long time because it deteriorates with age due to ultraviolet rays contained in sunlight.
  • this solar cell 100 is well known in the art in that so-called reverse current flows, in which electrons emitted from the dye are not transported to the semiconductor layer 103 and diffuse to the electrolyte solution of the electrolyte layer 104 and other dyes. Have the following issues.
  • the reverse current is generated because the internal impedance of the solar cell 100 is large, and the size of the internal impedance depends on the physical distance (gap) between the counter electrode 105 and the semiconductor layer 103 and the electrolyte. Depends on the material. Therefore, for example, if the container is a flat plate, it is easy to fill the electrolyte solution, and the gap length can be solved by using an insulator or the like formed into a film.
  • the size of (gap) is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, but it is difficult to form such a minute gap.
  • the object of the present invention is to solve the problem of aging degradation using a glass sealing structure in view of the above-mentioned problems of the prior art, and even if the container is tubular, the physical relationship between the counter electrode and the photoelectrode is
  • An object of the present invention is to provide a dye-sensitized solar cell that can maintain the size of a short distance (gap) at 50 ⁇ m or less and can suppress generation of a reverse current.
  • the present invention employs the following means in order to solve the above problems.
  • the first means is a transparent conductive film formed on the inner surface of a tubular container made of transparent glass, a photoelectrode which is a semiconductor film formed on the transparent conductive film and adsorbed with a dye, and the photoelectrode
  • the counter electrode is formed on a coiled substrate made of a metal material and an outer peripheral surface of the coiled substrate.
  • a dye-sensitized solar cell comprising: an electrode portion provided; and an insulator portion formed on an outer peripheral surface of the coil-shaped substrate so as to protrude radially outward from the electrode portion.
  • a second means is the electrode according to the first means, wherein the insulator portion is made of insulator particles, and is present between the insulator particles and is present on the surface of the coiled substrate and having a diameter smaller than the particle diameter of the insulator particles.
  • the dye-sensitized solar cell is characterized in that an electrode portion is formed of particles.
  • a third means is the dye-sensitized solar cell according to the first means, wherein the coiled substrate has a shape obtained by winding a wide surface of a band-shaped member as an outer peripheral surface.
  • a groove for exposing the coiled base is formed in the insulator portion formed on the outer peripheral surface, and the electrode portion is formed on the bottom surface of the groove. This is a dye-sensitized solar cell.
  • the counter electrode and the photoelectrode are not short-circuited because the insulator portion is provided on the photoelectrode side of the counter electrode.
  • the counter electrode is expanded or contracted by heat or the like, it is formed in a coil shape, so that it has elasticity and absorbs the expansion difference, so the distance (gap) between the photoelectrode and the counter electrode can be increased. It can be kept at a suitable value, for example 1-50 ⁇ m.
  • (A) is a plan sectional view of the dye-sensitized solar cell according to the first embodiment, (b) is a front sectional view, and (c) is a sectional view taken along the line A-A ′ of (a).
  • (A) is the enlarged view for description of the location of the code
  • It is front sectional drawing of the dye-sensitized solar cell which concerns on 2nd Embodiment.
  • (A)-(d) is a figure which shows the method of forming an insulator layer and an electrode layer on a counter electrode in order of a process.
  • (A) is a cross-sectional view of the dye-sensitized solar cell disclosed in Patent Document 1 cut in the tube axis direction, and (b) is a cross-sectional view taken along the line Z-Z ′ of (a).
  • FIGS. 1A is a plan sectional view of a dye-sensitized solar cell according to this embodiment
  • FIG. 1B is a front sectional view of the dye-sensitized solar cell according to this embodiment
  • FIG. 1 is a cross-sectional view taken along line AA ′ of FIG.
  • a transparent conductive film 12 is formed on the inner surface of a translucent tubular container 11, and a photoelectrode 13 is formed on the transparent conductive film 12. ing.
  • the transparent conductive film 12 extends into the sealing portion 20 and is connected to the metal foil 23 embedded in the sealing portion 20 so that electrons generated in the photoelectrode 13 are led out of the tube.
  • a current path is formed through the external lead 24 connected to the metal foil 23.
  • the counter electrode 15 is provided so as to be separated from the photoelectrode 13, and the internal lead 17 extending from the counter electrode 15 is connected to the metal foil 18 embedded in the sealing portion 16 and connected to the metal foil 18.
  • a current path is led out to the outside of the tube through the external lead 19.
  • the electrolytic solution 14 is filled between the photoelectrode 13 and the counter electrode 15, and the tubular container 11 has sealing portions 16 and 20 that are pinch-sealed at both ends so that the electrolytic solution 14 does not leak to the outside. is doing.
  • the tubular container 11 has sealing portions 16 and 20 that are pinch-sealed at both ends so that the electrolytic solution 14 does not leak to the outside. is doing.
  • the translucent tubular container 11 for example, a glass tube is used.
  • the glass material include quartz glass and soda glass.
  • the tube may have an elliptical or rectangular cross section.
  • the tubular container 11 can receive light from a direction of approximately 360 °, and the incident angle changes due to the movement of the sun. However, it has the advantage that sunlight can be evenly incident.
  • the transparent conductive film 12 is formed on the inner surface of the tubular container 11 and has a light-transmitting performance for transmitting light to the photoelectrode 13, and is used to lead out the current generated from the photoelectrode 13 to the outside of the tube. It is an electric circuit. As shown in FIG. 1B, the transparent conductive film 12 formed on the inner surface of the tubular container 11 extends into one sealing portion 20 and is electrically connected to the metal foil 23 by a pinch seal. , Connected to the external lead 24 through the metal foil 23 and led out of the tube.
  • the photoelectrode 13 is composed of a semiconductor particle deposition layer containing particles such as titanium oxide (TiO 2 ), tin oxide, zinc oxide, niobium oxide, tantalum oxide, and zirconium oxide, and is formed on the transparent conductive film 12.
  • a photosensitizing dye made of an organic dye such as a ruthenium complex is attached (supported) to the particles.
  • FIG. 2A is an explanatory diagram showing an enlargement of the portion indicated by the symbol A shown in FIG.
  • the counter electrode 15 is made of a metal wire coil (elastic body) such as stainless steel, and as shown in FIG. 2 (a), a metal wire coil ( On the surface of the metal base 151 of the elastic body, the particle size of the insulator particles (insulator part) 152 such as silica (SiO 2 ), alumina (Al 2 O 3 ), titanium oxide (TiO 2 ), etc.
  • Insulator particles 152 may be porous or non-porous. However, when porous particles are used, the electrolyte solution easily passes through the pores, and the redox reaction is improved. Can do.
  • the distance (gap) between the photoelectrode 13 formed by the insulator particles 152 and the metal substrate 151 is preferably in the range of 1 to 50 ⁇ m.
  • the deposition layer 154 of the counter electrode 15 contains the insulator particles 152
  • the difficulty of providing an insulator on the inner surface of the tubular container 11 can be solved.
  • the metal substrate 151 made of a metal wire coil (elastic body) is platinum, silica (SiO 2 ), alumina (Al 2 O 3 ), There is no need to provide insulator particles 152 such as titanium oxide (TiO 2 ) and electrode particles such as platinum having a catalytic function.
  • a method for forming the deposition layer 154 on the metal substrate 151 will be described.
  • a slurry (suspension) is made of two kinds of particles, that is, insulator particles such as alumina particles and electrode particles such as platinum particles, in which the particle size of the insulator particles is larger than that of the electrode particles and a liquid.
  • slurry is applied to a part of the surface of the metal substrate 151 made of a linear or thin rod-shaped member. Since the electrode particles 153 having a small particle size are deposited on the surface of the metal substrate 151 relative to the insulator particles 152, the electrode particles 153 are fired after being deposited.
  • the metal substrate 151 After firing, the metal substrate 151 is wound so that the slurry application surface is positioned on the outer peripheral surface to produce a metal wire coil.
  • a method of forming a slurry application layer on the surface of a metal substrate there are methods such as applying the slurry in a mist form by spraying or applying it with a brush.
  • electrolytic solution 14 for example, a so-called redox electrolytic solution in which iodine and iodide are combined is used.
  • the sealing parts 16 and 20 are formed by pinch sealing by heating the end part of the tubular container 11, and therefore both end parts of the tubular container 11 are hermetically sealed by the sealing parts 16 and 20. .
  • One end of the coil made of metal wire which is the counter electrode 15 is connected to one end of the internal lead 17, and the other end of the internal lead 17 is connected to the external lead 19 through the metal foil 18 in the sealing portion 16, and outside the tube. Derived.
  • the other end of the metal wire coil is mechanically connected to the internal lead 22 and the metal foil 23 in the sealing portion 20 via the insulating and supporting member 21 and supported by the sealing portion 20.
  • the coil-shaped substrate is, for example, a resin material having elasticity such as PET (polyethylene terephthalate), PP (polypropylene) and the like, and the surface thereof is coated with a metal film. Can also be used.
  • a resin material having elasticity such as PET (polyethylene terephthalate), PP (polypropylene) and the like, and the surface thereof is coated with a metal film. Can also be used.
  • the material of the electrode particles having a catalytic function may be gold, silver, copper, carbon or the like having a small ionization tendency in addition to platinum.
  • these plural types of particles may be attached to the coiled substrate in order to improve electrical contact.
  • FIG. 3 is a front sectional view of the dye-sensitized solar cell according to the present embodiment.
  • the dye-sensitized solar cell 1 of the present embodiment uses the strip-shaped metal coil as the counter electrode 25 in place of the metal wire coil, and thus the dye of the first embodiment.
  • the configuration is different from that of the sensitized solar cell, the other configuration corresponds to the configuration of the same symbol shown in FIG. In this case as well, an insulator portion is formed in the outer peripheral direction on a part of the surface of the coiled substrate as in FIG.
  • the strip-shaped metal coil to be the counter electrode 25 is wound in a cylindrical shape so that the surface in the longitudinal direction of the cross-section of the strip-shaped metal material becomes the outer peripheral surface to form a coil.
  • FIG. 4 is a diagram illustrating a method for forming a deposited layer on the counter electrode 25.
  • a band-shaped metal material 251 is prepared, and as shown in FIG. 4B, the band-shaped metal material 251 is made of alumina particles or the like on the surface of the wide surface.
  • An insulator layer (insulator portion) 252 is formed.
  • a groove 253 that exposes the metal material 251 is formed along the longitudinal direction of the band-shaped metal material 251, and as shown in FIG.
  • an electrode layer (electrode part) 254 such as a platinum layer is formed on the bottom surface of the groove 253 by thermal spraying, electrolytic plating, or the like, and the insulator layer protrudes outward from the electrode layer.
  • the counter electrode 25 made of a strip-shaped metal coil is manufactured by winding the strip-shaped metal material so that the treated surface is positioned on the outer periphery.
  • belt-shaped metal material is platinum, it is not necessary to form electrode layers, such as a platinum layer.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

Disclosed is a pigment-sensitized photovoltaic cell that solves a problem of degradation over time by using glass in a seal, and maintains a size of a physical distance (gap) between an opposing electrode and a photoelectrode to 50 µm or less, and suppresses generation of an inverse current, even if a container is tube-shaped. A pigment-sensitized photovoltaic cell is equipped with a transparent conductive film 12 formed on an inner surface of a tube-shaped container 11 composed of a transparent glass; a photoelectrode 13 adhered thereto with pigment, formed on the transparent conductive film 12, and an opposing electrode 15 insulated with the photoelectrode 13. In the pigment-sensitized photovoltaic cell sealed with an electrolysis solution 14 inside the tube-shaped container 11, the opposing electrode 15 is characterized by being equipped with a coiled substrate composed of a metallic material; and electrode portion disposed on an external circumference of the coiled substrate; and the insulating portion is formed to project further outward in a radial direction than the electrode portion on the external circumference of the coiled substrate.

Description

色素増感太陽電池Dye-sensitized solar cell
　本発明は、色素増感型太陽電池に関する。特に、透光性の管状容器を有する色素増感太陽電池に関する。 The present invention relates to a dye-sensitized solar cell. In particular, it is related with the dye-sensitized solar cell which has a translucent tubular container.
　従来から、地球環境に対する影響の少ない新たなエネルギー源として太陽電池の開発が行われている。中でも、シリコン半導体を用いた太陽電池は、高い変換効率と優れた光安定性とを有しており、広く一般に普及している。しかしながら、製造に際して高温高真空の条件が必要であり、大面積化が容易ではなく製造コストが高いといった問題がある。 Conventionally, solar cells have been developed as a new energy source with little influence on the global environment. Among these, solar cells using silicon semiconductors have high conversion efficiency and excellent light stability, and are widely spread. However, high-temperature and high-vacuum conditions are required for production, and there is a problem that the area is not easily increased and the production cost is high.
　一方、透明な容器の内部に電解液を充填し、色素を吸着させた多孔質半導体からなる光電極と、対向電極とを設け、太陽光が照射された色素が電子を放出して、電気エネルギーを取り出すことができる色素増感型太陽電池が知られている（特許文献１）。この種の太陽電池は、製造のために高真空なチャンバー等が不要であり、設備面での負担が少なく安価に製造できるという利点がある。 On the other hand, a photoelectrode made of a porous semiconductor filled with an electrolytic solution and adsorbed with a dye inside a transparent container and a counter electrode are provided, and the dye irradiated with sunlight emits electrons to generate electric energy. There is known a dye-sensitized solar cell that can take out the water (Patent Document 1). This type of solar cell does not require a high-vacuum chamber or the like for manufacturing, and has the advantage that it can be manufactured inexpensively with less burden on the equipment.
　図５（ａ）は、特許文献１に示された色素増感型太陽電池の管軸方向で切断した断面図、図５（ｂ）は、図５（ａ）のＺ－Ｚ’線断面図である。
　これらの図に示すように、太陽電池１００は、透明材料からなる管１０１の内面に、透明導電層１０２、色素を吸着させた色素増感多孔質半導体層１０３、及び電解質層１０４が順次設けられており、管１０１の内部には管軸に沿って対極１０５が挿入されている。対極１０５の一端部１０５ｂは管１０１より外方に突出している。管１０１の一端部１０１ｂと対極１０５の一端部１０５ｂとの間、及び管１０１の他端部１０１ａと対極１０５の他端部１０５ａとの間は、例えば、エポキシ樹脂からなる封止部材１０６により、絶縁されると共に封止され、電解質層１０４の電解液が管１０１の外部に漏れないようになっている。対極１０５および透明導電層１０２には、それぞれリード線１０７、１０８が接続されている。 FIG. 5 (a) is a cross-sectional view of the dye-sensitized solar cell disclosed in Patent Document 1 cut in the tube axis direction, and FIG. 5 (b) is a cross-sectional view taken along the line ZZ ′ of FIG. 5 (a). It is.
As shown in these drawings, the solar cell 100 is provided with a transparent conductive layer 102, a dye-sensitized porous semiconductor layer 103 on which a dye is adsorbed, and an electrolyte layer 104 in this order on the inner surface of a tube 101 made of a transparent material. A counter electrode 105 is inserted into the tube 101 along the tube axis. One end 105 b of the counter electrode 105 protrudes outward from the tube 101. Between the one end portion 101b of the tube 101 and one end portion 105b of the counter electrode 105 and between the other end portion 101a of the tube 101 and the other end portion 105a of the counter electrode 105, for example, by a sealing member 106 made of epoxy resin, It is insulated and sealed so that the electrolyte solution in the electrolyte layer 104 does not leak out of the tube 101. Lead wires 107 and 108 are connected to the counter electrode 105 and the transparent conductive layer 102, respectively.
　この太陽電池１００に太陽光が照射されると、太陽光は、管１０１及び透明導電層１０２を透過して、色素増感多孔質半導体層１０３に到達し、光化学反応が生じて色素が電子を放出し、リード線１０７、１０８間に起電力が発生するものである。特に、この太陽電池１００は、容器が円管状であることにより、光の入射角度に対する発電量の変化を大幅に低減することができる。 When the solar cell 100 is irradiated with sunlight, the sunlight passes through the tube 101 and the transparent conductive layer 102 and reaches the dye-sensitized porous semiconductor layer 103, where a photochemical reaction occurs and the dye emits electrons. The electromotive force is generated between the lead wires 107 and 108. In particular, in the solar cell 100, since the container is circular, the change in the amount of power generation with respect to the incident angle of light can be greatly reduced.
特開２００７－１２５４５号公報JP 2007-12545 A 特開２００８－１９２６０３号公報JP 2008-192603 A
　しかしながら、特許文献１記載の太陽電池１００では、管１０１の両端を封止する封止部材１０６としてエポキシ等の樹脂が用いられている。このように、管１０１と封止部材１０６が別部材から構成されると、封止の気密性が十分ではない。また、封止部材１０６に用いられるエポキシ樹脂は、太陽光に含まれる紫外線により経年劣化するために長期間にわたって使用することができないという問題がある。また、この太陽電池１００は、色素から放出される電子が、半導体層１０３に輸送されずに、電解質層１０４の電解液や他の色素へ拡散してしまうという、いわゆる逆電流が流れるという従来周知の課題を有している。つまり、逆電流が発生するのは、太陽電池１００の内部インピーダンスが大きいためであり、この内部インピーダンスの大きさは、対極１０５と半導体層１０３間の物理的な距離（ギャップ）の大きさや電解質の材料に依存する。そのため、例えば、容器が平板状であれば、電解液の充填が容易であり、ギャップ長も成膜した絶縁体等を利用して解決することが可能であるが、容器が管状の場合、距離（ギャップ）の大きさは１００μｍ以下が好ましく、さらには５０μｍ以下がより好ましいが、このような微小なギャップを形成することが困難である。 However, in the solar cell 100 described in Patent Document 1, a resin such as epoxy is used as the sealing member 106 that seals both ends of the tube 101. Thus, when the pipe | tube 101 and the sealing member 106 are comprised from another member, the airtightness of sealing is not enough. In addition, the epoxy resin used for the sealing member 106 has a problem that it cannot be used for a long time because it deteriorates with age due to ultraviolet rays contained in sunlight. Further, this solar cell 100 is well known in the art in that so-called reverse current flows, in which electrons emitted from the dye are not transported to the semiconductor layer 103 and diffuse to the electrolyte solution of the electrolyte layer 104 and other dyes. Have the following issues. That is, the reverse current is generated because the internal impedance of the solar cell 100 is large, and the size of the internal impedance depends on the physical distance (gap) between the counter electrode 105 and the semiconductor layer 103 and the electrolyte. Depends on the material. Therefore, for example, if the container is a flat plate, it is easy to fill the electrolyte solution, and the gap length can be solved by using an insulator or the like formed into a film. The size of (gap) is preferably 100 μm or less, more preferably 50 μm or less, but it is difficult to form such a minute gap.
　本発明の目的は、上記の従来技術の問題点に鑑みて、ガラス封止構造を用いて経年劣化の問題を解決すると共に、容器が管状であっても、対向電極と光電極間の物理的な距離（ギャップ）の大きさを５０μｍ以下に維持することができ、逆電流の発生を抑制することを可能にした色素増感太陽電池を提供することにある。 The object of the present invention is to solve the problem of aging degradation using a glass sealing structure in view of the above-mentioned problems of the prior art, and even if the container is tubular, the physical relationship between the counter electrode and the photoelectrode is An object of the present invention is to provide a dye-sensitized solar cell that can maintain the size of a short distance (gap) at 50 μm or less and can suppress generation of a reverse current.
　本発明は、上記の課題を解決するために、次のような手段を採用した。
　第１の手段は、透明なガラスよりなる管状容器の内面に形成された透明導電膜と、該透明導電膜上に形成された、色素が吸着された半導体膜である光電極と、該光電極と絶縁した対向電極とを備え、前記管状容器の内部に電解液が密封された色素増感太陽電池において、前記対向電極は、金属材からなるコイル状基体と、該コイル状基体の外周面に設けられた電極部と、前記コイル状基体の外周面に前記電極部よりも径方向外方に突出するように形成された絶縁体部を備えることを特徴とする色素増感太陽電池である。
　第２の手段は、第１の手段において、前記絶縁体部は絶縁体粒子よりなり、該絶縁体粒子間にあって前記コイル状基体の表面に存在する、前記絶縁体粒子の粒子径より小径の電極粒子により電極部が形成されていることを特徴とする色素増感太陽電池である。
　第３の手段は、第１の手段において、前記コイル状基体は、帯状部材の幅広の面を外周面として巻回した形状であることを特徴とする色素増感太陽電池である。
　第４の手段は、第３の手段において、前記外周面に形成された前記絶縁体部には、コイル状基体を露出させる溝が形成され、該溝の底面に前記電極部が形成されていることを特徴とする色素増感太陽電池である。 The present invention employs the following means in order to solve the above problems.
The first means is a transparent conductive film formed on the inner surface of a tubular container made of transparent glass, a photoelectrode which is a semiconductor film formed on the transparent conductive film and adsorbed with a dye, and the photoelectrode In the dye-sensitized solar cell in which the electrolyte solution is sealed inside the tubular container, the counter electrode is formed on a coiled substrate made of a metal material and an outer peripheral surface of the coiled substrate. A dye-sensitized solar cell, comprising: an electrode portion provided; and an insulator portion formed on an outer peripheral surface of the coil-shaped substrate so as to protrude radially outward from the electrode portion.
A second means is the electrode according to the first means, wherein the insulator portion is made of insulator particles, and is present between the insulator particles and is present on the surface of the coiled substrate and having a diameter smaller than the particle diameter of the insulator particles. The dye-sensitized solar cell is characterized in that an electrode portion is formed of particles.
A third means is the dye-sensitized solar cell according to the first means, wherein the coiled substrate has a shape obtained by winding a wide surface of a band-shaped member as an outer peripheral surface.
According to a fourth means, in the third means, a groove for exposing the coiled base is formed in the insulator portion formed on the outer peripheral surface, and the electrode portion is formed on the bottom surface of the groove. This is a dye-sensitized solar cell.
　本発明によれば、対向電極が光電極に接近して対向しても、対向電極の光電極側に絶縁体部が設けられているので、対向電極と光電極は短絡することが無い。また、対向電極は熱等によって膨張収縮しても、コイル状に形成されているので、弾性を有し、膨張差を吸収するので、光電極と対向電極間の距離（ギャップ）の大きさを適切な値、例えば１～５０μｍに保持することができる。 According to the present invention, even if the counter electrode approaches and opposes the photoelectrode, the counter electrode and the photoelectrode are not short-circuited because the insulator portion is provided on the photoelectrode side of the counter electrode. In addition, even if the counter electrode is expanded or contracted by heat or the like, it is formed in a coil shape, so that it has elasticity and absorbs the expansion difference, so the distance (gap) between the photoelectrode and the counter electrode can be increased. It can be kept at a suitable value, for example 1-50 μm.
（ａ）は第１の実施形態に係る色素増感太陽電池の平面断面図、（ｂ）は正面断面図、及び（ｃ）は（ａ）のＡ－Ａ’線断面図である。(A) is a plan sectional view of the dye-sensitized solar cell according to the first embodiment, (b) is a front sectional view, and (c) is a sectional view taken along the line A-A ′ of (a). （ａ）は図１に示した符号Ａの箇所の説明用拡大図、及び（ｂ）は（ａ）と異なる形態における説明用拡大図である。(A) is the enlarged view for description of the location of the code | symbol A shown in FIG. 1, (b) is the enlarged view for description in the form different from (a). 第２の実施形態に係る色素増感太陽電池の正面断面図である。It is front sectional drawing of the dye-sensitized solar cell which concerns on 2nd Embodiment. （ａ）～（ｄ）は対向電極上に絶縁体層及び電極層を形成する方法を工程順に示す図である。(A)-(d) is a figure which shows the method of forming an insulator layer and an electrode layer on a counter electrode in order of a process. （ａ）は特許文献１に示された色素増感型太陽電池の管軸方向で切断した断面図、及び（ｂ）は（ａ）のＺ－Ｚ’線断面図である。(A) is a cross-sectional view of the dye-sensitized solar cell disclosed in Patent Document 1 cut in the tube axis direction, and (b) is a cross-sectional view taken along the line Z-Z ′ of (a).
　本発明の第１の実施形態を図１及び図２を用いて説明する。
　図１（ａ）は、本実施形態に係る色素増感太陽電池の平面断面図、図１（ｂ）は本実施形態に係る色素増感太陽電池の正面断面図、図１（ｃ）は図１（ａ）のＡ－Ａ’線断面図である。
　これらの図に示すように、色素増感太陽電池１は、透光性の管状容器１１の内面に、透明導電膜１２が形成されており、透明導電膜１２上には光電極１３が形成されている。光電極１３で発生した電子が管外に導出されるように、透明導電膜１２は、封止部２０内にまで延在しており、封止部２０内に埋設された金属箔２３に接続され、金属箔２３に接続された外部リード２４を介し電流路が形成されている。一方、光電極１３と離間するように対向電極１５が設けられており、対向電極１５から延びる内部リード１７が封止部１６内に埋設された金属箔１８に接続され、金属箔１８に接続された外部リード１９を介し電流路が管外まで導出されている。また、光電極１３と対向電極１５の間には電解液１４が充填されており、管状容器１１は電解液１４が外部に漏れないように両端にピンチシールされた封止部１６、２０を有している。以下に、色素増感太陽電池１の各構成について詳述する。 A first embodiment of the present invention will be described with reference to FIGS.
1A is a plan sectional view of a dye-sensitized solar cell according to this embodiment, FIG. 1B is a front sectional view of the dye-sensitized solar cell according to this embodiment, and FIG. 1 is a cross-sectional view taken along line AA ′ of FIG.
As shown in these drawings, in the dye-sensitized solar cell 1, a transparent conductive film 12 is formed on the inner surface of a translucent tubular container 11, and a photoelectrode 13 is formed on the transparent conductive film 12. ing. The transparent conductive film 12 extends into the sealing portion 20 and is connected to the metal foil 23 embedded in the sealing portion 20 so that electrons generated in the photoelectrode 13 are led out of the tube. Thus, a current path is formed through the external lead 24 connected to the metal foil 23. On the other hand, the counter electrode 15 is provided so as to be separated from the photoelectrode 13, and the internal lead 17 extending from the counter electrode 15 is connected to the metal foil 18 embedded in the sealing portion 16 and connected to the metal foil 18. A current path is led out to the outside of the tube through the external lead 19. In addition, the electrolytic solution 14 is filled between the photoelectrode 13 and the counter electrode 15, and the tubular container 11 has sealing portions 16 and 20 that are pinch-sealed at both ends so that the electrolytic solution 14 does not leak to the outside. is doing. Below, each structure of the dye-sensitized solar cell 1 is explained in full detail.
　透光性の管状容器１１としては、例えば、ガラス製の管が用いられる。ガラスの材料としては、例えば、石英ガラス、ソーダガラスである。管の断面は、円管状以外にも、断面が楕円形、矩形でもよく、管状容器１１によれば、ほぼ３６０°の方向からの光を受けることができ、太陽の移動によって入射角が変わっても、満遍なく太陽光を入射することができるという利点を有する。 As the translucent tubular container 11, for example, a glass tube is used. Examples of the glass material include quartz glass and soda glass. In addition to the circular tube, the tube may have an elliptical or rectangular cross section. The tubular container 11 can receive light from a direction of approximately 360 °, and the incident angle changes due to the movement of the sun. However, it has the advantage that sunlight can be evenly incident.
　透明導電膜１２の材料としては、ＩＴＯ（酸化インジウムスズ）、ＦＴＯ（フッ素ドープ酸化スズ）、ＺｎＯ（酸化亜鉛）等が用いられる。透明導電膜１２は、管状容器１１の内面に成膜されており、光電極１３まで光を透過させるために透光性能を有し、光電極１３から発生する電流を管外に導出するための電路になっている。管状容器１１の内面に形成された透明導電膜１２は、図１（ｂ）に示すように、一方の封止部２０内に延在して、ピンチシールによって金属箔２３に電気的に接続され、金属箔２３を介して外部リード２４に接続され、管外に導出されている。 As the material of the transparent conductive film 12, ITO (indium tin oxide), FTO (fluorine-doped tin oxide), ZnO (zinc oxide) or the like is used. The transparent conductive film 12 is formed on the inner surface of the tubular container 11 and has a light-transmitting performance for transmitting light to the photoelectrode 13, and is used to lead out the current generated from the photoelectrode 13 to the outside of the tube. It is an electric circuit. As shown in FIG. 1B, the transparent conductive film 12 formed on the inner surface of the tubular container 11 extends into one sealing portion 20 and is electrically connected to the metal foil 23 by a pinch seal. , Connected to the external lead 24 through the metal foil 23 and led out of the tube.
　光電極１３は、酸化チタン（ＴｉＯ2 ）、酸化スズ、酸化亜鉛、酸化ニオブ、酸化タンタル、酸化ジルコニウム等の粒子を含有する半導体粒子堆積層からなり、透明導電膜１２上に形成されている。粒子にはルテニウム錯体等の有機色素からなる光増感色素が付着（担持）されている。 The photoelectrode 13 is composed of a semiconductor particle deposition layer containing particles such as titanium oxide (TiO 2 ), tin oxide, zinc oxide, niobium oxide, tantalum oxide, and zirconium oxide, and is formed on the transparent conductive film 12. A photosensitizing dye made of an organic dye such as a ruthenium complex is attached (supported) to the particles.
　図２（ａ）は、図１（ｂ）に示した符号Ａの箇所を拡大して示した説明図である。図１（ａ）、（ｂ）に示すように、対向電極１５は、ステンレス鋼等の金属ワイヤー製コイル（弾性体）で構成され、図２（ａ）に示すように、金属ワイヤー製コイル（弾性体）の金属基体１５１の表面には、シリカ（ＳｉＯ2 ）、アルミナ（Ａｌ2 Ｏ3 ）、酸化チタン（ＴｉＯ2 ）等の絶縁体粒子（絶縁体部）１５２と絶縁体粒子より粒径が小さい触媒機能を有する白金等のイオン化傾向の小さい、電極粒子（電極部）１５３からなる堆積層１５４が金属基体１５１の外周方向の表面の一部に形成されている。絶縁体粒子１５２は、多孔質のもの又は多孔質でないものが利用されるが、多孔質のものを利用した場合には、孔を通って電解液が通り易くなり、レドックス反応を良好化することができる。絶縁体粒子１５２によって形成される光電極１３と金属基体１５１の距離（ギャップ）の大きさは、１～５０μｍの範囲のものが好ましい。対向電極１５の堆積層１５４が絶縁体粒子１５２を含有することによって、管状容器１１の内面に絶縁体を設けることの困難性を解決することができる。
　図２（ｂ）に示すように、金属ワイヤー製コイル（弾性体）からなる金属基体１５１が白金である場合には、基体表面には、シリカ（ＳｉＯ2 ）、アルミナ（Ａｌ2 Ｏ3 ）、酸化チタン（ＴｉＯ2 ）等の絶縁体粒子１５２を設け、触媒機能を有する白金等の電極粒子を設ける必要はない。 FIG. 2A is an explanatory diagram showing an enlargement of the portion indicated by the symbol A shown in FIG. As shown in FIGS. 1 (a) and 1 (b), the counter electrode 15 is made of a metal wire coil (elastic body) such as stainless steel, and as shown in FIG. 2 (a), a metal wire coil ( On the surface of the metal base 151 of the elastic body, the particle size of the insulator particles (insulator part) 152 such as silica (SiO 2 ), alumina (Al 2 O 3 ), titanium oxide (TiO 2 ), etc. A deposition layer 154 made of electrode particles (electrode part) 153 with a small ionization tendency, such as platinum having a small catalytic function, is formed on a part of the outer peripheral surface of the metal substrate 151. Insulator particles 152 may be porous or non-porous. However, when porous particles are used, the electrolyte solution easily passes through the pores, and the redox reaction is improved. Can do. The distance (gap) between the photoelectrode 13 formed by the insulator particles 152 and the metal substrate 151 is preferably in the range of 1 to 50 μm. When the deposition layer 154 of the counter electrode 15 contains the insulator particles 152, the difficulty of providing an insulator on the inner surface of the tubular container 11 can be solved.
As shown in FIG. 2B, when the metal substrate 151 made of a metal wire coil (elastic body) is platinum, silica (SiO 2 ), alumina (Al 2 O 3 ), There is no need to provide insulator particles 152 such as titanium oxide (TiO 2 ) and electrode particles such as platinum having a catalytic function.
　金属基体１５１上に堆積層１５４を形成する方法を説明する。初めに、絶縁体粒子例えばアルミナ粒子と、電極粒子例えば白金粒子の２種類の粒子であって、絶縁体粒子の粒径サイズが電極粒子より大きい粒子と液体によりスラリー（懸濁液）をつくる。次に、線状ないし細い棒状部材からなる金属基体１５１の表面の一部にスラリーを塗布する。粒径の小さい電極粒子１５３は絶縁体粒子１５２よりも金属基体１５１表面側に沈着するので、沈着後、焼成する。焼成後、金属基体１５１を、スラリーの塗布面が外周面に位置されるように巻回して金属ワイヤー製コイルを作製する。その他に、金属基体の表面にスラリーの塗布層を形成する方法としては、スラリーをスプレーにて霧状に塗布したり、刷毛で塗布する等の方法がある。 A method for forming the deposition layer 154 on the metal substrate 151 will be described. First, a slurry (suspension) is made of two kinds of particles, that is, insulator particles such as alumina particles and electrode particles such as platinum particles, in which the particle size of the insulator particles is larger than that of the electrode particles and a liquid. Next, slurry is applied to a part of the surface of the metal substrate 151 made of a linear or thin rod-shaped member. Since the electrode particles 153 having a small particle size are deposited on the surface of the metal substrate 151 relative to the insulator particles 152, the electrode particles 153 are fired after being deposited. After firing, the metal substrate 151 is wound so that the slurry application surface is positioned on the outer peripheral surface to produce a metal wire coil. In addition, as a method of forming a slurry application layer on the surface of a metal substrate, there are methods such as applying the slurry in a mist form by spraying or applying it with a brush.
　電解液１４としては、例えば、ヨウ素とヨウ化物等を組み合わせた、いわゆるレドックス電解液を使用する。 As the electrolytic solution 14, for example, a so-called redox electrolytic solution in which iodine and iodide are combined is used.
　封止部１６、２０は、管状容器１１の端部を加熱してピンチシールによって形成されており、そのため、管状容器１１の両端部は、封止部１６、２０によって気密に封止されている。 The sealing parts 16 and 20 are formed by pinch sealing by heating the end part of the tubular container 11, and therefore both end parts of the tubular container 11 are hermetically sealed by the sealing parts 16 and 20. .
　対向電極１５である金属ワイヤー製コイルの一端は、内部リード１７の一端に接続され、内部リード１７の他端は封止部１６において金属箔１８を介して外部リード１９に接続され、管外に導出される。金属ワイヤー製コイルの他端は、絶縁兼支持部材２１を介して内部リード２２、封止部２０における金属箔２３に機械的に接続されて、封止部２０に支持される。 One end of the coil made of metal wire which is the counter electrode 15 is connected to one end of the internal lead 17, and the other end of the internal lead 17 is connected to the external lead 19 through the metal foil 18 in the sealing portion 16, and outside the tube. Derived. The other end of the metal wire coil is mechanically connected to the internal lead 22 and the metal foil 23 in the sealing portion 20 via the insulating and supporting member 21 and supported by the sealing portion 20.
　なお、コイル状基体としては、金属製のものの他に、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＰ（ポリプロピレン）等の弾性を有する樹脂材料をコイル状に成型してその表面に金属被膜をコートしたものを用いることもできる。 In addition to the metal substrate, the coil-shaped substrate is, for example, a resin material having elasticity such as PET (polyethylene terephthalate), PP (polypropylene) and the like, and the surface thereof is coated with a metal film. Can also be used.
　触媒機能を有する電極粒子の材質は、白金のほかに、イオン化傾向の小さい金、銀、銅、炭素などでもよい。電極粒子をコイル状基体に付着させる場合には、電気的接触を良好にするためにこれらの複数種類の粒子を用いてコイル状基体に付着させてもよい。 The material of the electrode particles having a catalytic function may be gold, silver, copper, carbon or the like having a small ionization tendency in addition to platinum. When the electrode particles are attached to the coiled substrate, these plural types of particles may be attached to the coiled substrate in order to improve electrical contact.
　次に、本発明の第２の実施形態を図３及び図４を用いて説明する。
　図３は、本実施形態に係る色素増感太陽電池の正面断面図である。
　同図に示すように、本実施形態の色素増感太陽電池１は、対向電極２５として、金属ワイヤー製コイルに代えて、帯状の金属製コイルを用いた点で、第１の実施形態の色素増感太陽電池と構成が相違するが、その他の構成は、図１に示した同符号の構成に対応するので説明を省略する。この場合も図１と同様にコイル状基体の表面の一部に、外周方向に絶縁体部が形成されている。 Next, a second embodiment of the present invention will be described with reference to FIGS.
FIG. 3 is a front sectional view of the dye-sensitized solar cell according to the present embodiment.
As shown in the figure, the dye-sensitized solar cell 1 of the present embodiment uses the strip-shaped metal coil as the counter electrode 25 in place of the metal wire coil, and thus the dye of the first embodiment. Although the configuration is different from that of the sensitized solar cell, the other configuration corresponds to the configuration of the same symbol shown in FIG. In this case as well, an insulator portion is formed in the outer peripheral direction on a part of the surface of the coiled substrate as in FIG.
　対向電極２５となる帯状の金属製コイルは、帯状の金属材の断面長手方向の面が外周面となるように、円筒状に巻いてコイルを形成する。対向電極２５を帯状の金属製コイルとすることによって、光電極１３と対向する面積が、断面形状が円形状であるワイヤーコイルに比べて大きくなる利点がある。 The strip-shaped metal coil to be the counter electrode 25 is wound in a cylindrical shape so that the surface in the longitudinal direction of the cross-section of the strip-shaped metal material becomes the outer peripheral surface to form a coil. By making the counter electrode 25 into a strip-shaped metal coil, there is an advantage that the area facing the photoelectrode 13 is larger than that of a wire coil having a circular cross section.
　図４は、対向電極２５上に堆積層を形成する方法を示す図である。
　初めに、図４（ａ）に示すように、帯状の金属材２５１を用意し、図４（ｂ）に示すように、帯状の金属材２５１の幅広の面の表面上にアルミナ粒子等からなる絶縁体層（絶縁体部）２５２を形成する。次に、図４（ｃ）に示すように、帯状の金属材２５１の長手方向に沿って金属材２５１を露出させる溝２５３を形成し、図４（ｄ）に示すように、溝２５３の中に溶射、電解鍍金等によって白金層等の電極層（電極部）２５４を溝２５３の底面に形成し、絶縁体層が電極層より外方に突出した状態とする。前記の処理後、帯状の金属材の処理面が外周に位置されるように巻回して帯状の金属製コイルからなる対向電極２５を作製する。なお、帯状の金属材が白金である場合は、白金層等の電極層を形成する必要はない。 FIG. 4 is a diagram illustrating a method for forming a deposited layer on the counter electrode 25.
First, as shown in FIG. 4A, a band-shaped metal material 251 is prepared, and as shown in FIG. 4B, the band-shaped metal material 251 is made of alumina particles or the like on the surface of the wide surface. An insulator layer (insulator portion) 252 is formed. Next, as shown in FIG. 4C, a groove 253 that exposes the metal material 251 is formed along the longitudinal direction of the band-shaped metal material 251, and as shown in FIG. Then, an electrode layer (electrode part) 254 such as a platinum layer is formed on the bottom surface of the groove 253 by thermal spraying, electrolytic plating, or the like, and the insulator layer protrudes outward from the electrode layer. After the above treatment, the counter electrode 25 made of a strip-shaped metal coil is manufactured by winding the strip-shaped metal material so that the treated surface is positioned on the outer periphery. In addition, when a strip | belt-shaped metal material is platinum, it is not necessary to form electrode layers, such as a platinum layer.
１　色素増感太陽電池
１１　管状容器
１２　透明導電膜
１３　光電極
１４　電解液
１５　対向電極
１５１ 金属基体
１５２ 絶縁体粒子（絶縁体部）
１５３ 電極粒子（電極部）
１５４ 堆積層
１６、２０　封止部
１７、２２　内部リード
１８、２３　金属箔
１９、２４　外部リード
２１　絶縁兼支持部材
２５　対向電極
２５１　帯状金属材
２５２　絶縁体層（絶縁体部）
２５３　溝
２５４　電極層（電極部） DESCRIPTION OF SYMBOLS 1 Dye-sensitized solar cell 11 Tubular container 12 Transparent conductive film 13 Photoelectrode 14 Electrolyte 15 Counter electrode 151 Metal substrate 152 Insulator particle (insulator part)
153 Electrode particles (electrode part)
154 Deposition layers 16 and 20 Sealing portions 17 and 22 Internal leads 18 and 23 Metal foils 19 and 24 External leads 21 Insulating and supporting member 25 Counter electrode 251 Band-shaped metal material 252 Insulator layer (insulator portion)
253 Groove 254 Electrode layer (electrode part)

Claims (4)

  1. 　透明なガラスよりなる管状容器の内面に形成された透明導電膜と、該透明導電膜上に形成された、色素が吸着された半導体膜である光電極と、該光電極と絶縁した対向電極とを備え、前記管状容器の内部に電解液が密封された色素増感太陽電池において、
    　前記対向電極は、金属材からなるコイル状基体と、該コイル状基体の外周面に設けられた電極部と、前記コイル状基体の外周面に前記電極部よりも径方向外方に突出するように形成された絶縁体部を備えることを特徴とする色素増感太陽電池。     A transparent conductive film formed on the inner surface of a tubular container made of transparent glass, a photoelectrode which is a semiconductor film adsorbed with a dye formed on the transparent conductive film, and a counter electrode insulated from the photoelectrode; In a dye-sensitized solar cell in which an electrolytic solution is sealed inside the tubular container,
    The counter electrode includes a coiled base made of a metal material, an electrode portion provided on the outer peripheral surface of the coiled base, and an outer peripheral surface of the coiled base that protrudes radially outward from the electrode portion. A dye-sensitized solar cell, comprising an insulator portion formed on the surface.
  2. 　前記絶縁体部は絶縁体粒子よりなり、該絶縁体粒子間にあって前記コイル状基体の表面に存在する、前記絶縁体粒子の粒子径より小径の電極粒子により電極部が形成されていることを特徴とする請求項１に記載の色素増感太陽電池。 The insulator part is made of insulator particles, and the electrode part is formed by electrode particles having a diameter smaller than the particle diameter of the insulator particles existing between the insulator particles and on the surface of the coiled substrate. The dye-sensitized solar cell according to claim 1.
  3. 　前記コイル状基体は、帯状部材の幅広の面を外周面として巻回した形状であることを特徴とする請求項１に記載の色素増感太陽電池。 2. The dye-sensitized solar cell according to claim 1, wherein the coiled substrate has a shape in which a wide surface of a belt-shaped member is wound as an outer peripheral surface. 3.
  4. 　前記コイル状基体の外周面に形成された前記絶縁体部には、コイル状基体を露出させる溝が形成され、該溝の底面に前記電極部が形成されていることを特徴とする請求項３に記載の色素増感太陽電池。 4. The insulator portion formed on the outer peripheral surface of the coiled substrate is formed with a groove for exposing the coiled substrate, and the electrode portion is formed on a bottom surface of the groove. 2. A dye-sensitized solar cell according to 1.
PCT/JP2011/054867 2010-03-09 2011-03-03 Pigment-sensitized photovoltaic cell WO2011111592A1 (en)

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