WO2002005354A1 - Element de conversion photo-electrique solide, son procede de production, pile solaire pourvue d'un tel element de conversion photo-electrique solide, et dispositif d'alimentation en courant - Google Patents

Element de conversion photo-electrique solide, son procede de production, pile solaire pourvue d'un tel element de conversion photo-electrique solide, et dispositif d'alimentation en courant Download PDF

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Publication number
WO2002005354A1
WO2002005354A1 PCT/JP2001/005856 JP0105856W WO0205354A1 WO 2002005354 A1 WO2002005354 A1 WO 2002005354A1 JP 0105856 W JP0105856 W JP 0105856W WO 0205354 A1 WO0205354 A1 WO 0205354A1
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WIPO (PCT)
Prior art keywords
photoelectric conversion
power supply
solid
conversion element
compound
Prior art date
Application number
PCT/JP2001/005856
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English (en)
Japanese (ja)
Inventor
Masahiro Kobashi
Takayuki Aoshima
Yuki Tanaka
Shuichi Maeda
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Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000272006A external-priority patent/JP2002083635A/ja
Priority claimed from JP2000278322A external-priority patent/JP2002093472A/ja
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Priority to AU2001269457A priority Critical patent/AU2001269457A1/en
Publication of WO2002005354A1 publication Critical patent/WO2002005354A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • 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
    • Y02E10/549—Organic PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Solid-state photoelectric conversion element manufacturing method thereof, solar cell using solid-state photoelectric conversion element, and power supply
  • the present invention relates to a solid-state photoelectric conversion element containing a solid substance as a component, a solar cell using the element, a method for manufacturing the same, and an apparatus using the same.
  • the maximum energy conversion efficiency of monocrystalline silicon solar cells in solar cells using silicon is about 20%
  • amorphous silicon is about 20%
  • a maximum energy conversion efficiency of 10 to 12.5% has been achieved in solar cells, and research and development for application to high power use is becoming more active.
  • silicon-based solar cells require a lot of energy to produce the metal silicon, which is the raw material, which increases the production cost and also recovers the energy required for the production.
  • the required period energy payback time
  • silicon for photovoltaic cells generally uses residual materials from the process of manufacturing silicon for semiconductors, so there is a limit to the absolute amount, and this is affected by trends in demand in the semiconductor industry.
  • silane gas supply required in the manufacturing process of amorphous silicon solar cells.
  • compound semiconductors such as dominate and indium copper selenide has become active.
  • organic solar cells using organic substances and organic-inorganic hybrid solar cells combining organic and inorganic substances are expected to be cheaper and have a larger area. Is being done.
  • An object of the present invention is to provide a high energy conversion efficiency even under a low light amount, excellent long-term stability,
  • An object of the present invention is to provide a solid-state photoelectric conversion element which is less restricted in element design, has excellent productivity, and is suitable for reduction in size and weight.
  • Another object of the present invention is to provide a method for manufacturing a solid-state photoelectric conversion element that can easily manufacture the solid-state photoelectric conversion element.
  • Another object of the present invention is to provide a solar cell and a power supply using the solid-state photoelectric conversion element. Disclosure of the invention
  • a layer of the solid electrolyte itself has good electrical connection in the solid electrolyte, has a sufficient hole transport ability, and is formed up to the upper surface of the photosensitized electrode.
  • this layer can be used as a counter electrode, and it has been found that an element having such a configuration is useful as a photoelectric conversion element such as a solar cell, and the present invention has been completed.
  • a first gist of the present invention resides in a solid-state photoelectric conversion element having a solid substance that also serves as a hole transport layer and a hole current collecting electrode.
  • the second aspect of the present invention a metal oxide, formed from a solid material containing a light ⁇ compound and ⁇ -conjugated compound, the surface resistivity of the outermost surface of the solid material following 1 0 3 ⁇ / mouth In the solid-state photoelectric conversion element.
  • a third gist of the present invention is a solid formed from a single cell or a plurality of single cell elements, and having a light transmittance of 5% or more when the single cell element is irradiated with light having a wavelength of 500 nm. It exists in photoelectric conversion elements.
  • a fourth gist of the present invention resides in a solid-state photoelectric conversion element formed of one or more single cell elements, and the single cell element has flexibility with respect to at least two axes on an electrode plane.
  • Another gist of the present invention is that after impregnating a solution containing a ⁇ -conjugated compound and / or a complex compound composed of a conjugated compound and a metal element into pores of a metal oxide having a photosensitizing compound on its surface.
  • the present invention relates to a method for manufacturing a solid-state photoelectric conversion element, in which a solvent is removed to form a solid substance layer containing a complex compound comprising a ⁇ -conjugated compound and / or a concomitant compound and a metal element up to the outermost surface.
  • Another aspect of the present invention is to impregnate a solution containing a monomer that forms a ⁇ -conjugated polymer, a polymerization catalyst, and a compound that reduces the polymerization rate into pores of a metal oxide having a photosensitizing compound on its surface. And then polymerizing to form a solid material layer containing a ⁇ -conjugated polymer up to the outermost surface.
  • Another aspect of the present invention resides in a solar cell using the solid-state photoelectric conversion element and a power supply device using the solar cell.
  • a photoelectric conversion electrode having, as a constituent element, a photosensitizing electrode in which a dye is supported on an electrode surface having a pore structure formed by sintering oxide fine particles. It has been found that the use of the electric double-layer capacitor is small because the energy efficiency is high even when the element is low in illuminance, and the electric double layer capacitor can be charged. The inventors have found that the driving time of the secondary battery can be extended, and completed the present invention.
  • another gist of the present invention is to provide a portable power supply device having at least a photoelectric conversion element and a storage capacitor connected to a secondary battery for driving a portable electronic device, wherein the photoelectric conversion element has a transparent conductive property.
  • Another aspect of the present invention is a vehicle power supply device having at least a photoelectric conversion module and a storage capacitor electrically connected to a battery mounted on the vehicle, wherein the photoelectric conversion element forming the photoelectric conversion module is A transparent conductive electrode, an electron transport layer made of oxide fine particles having a pore structure, a hole transport layer, a hole current collecting electrode, and a photosensitizing compound attached or fixed to the electron transport layer.
  • the vehicle power supply system having at least a photoelectric conversion module and a storage capacitor electrically connected to a battery mounted on the vehicle, wherein the photoelectric conversion element forming the photoelectric conversion module is A transparent conductive electrode, an electron transport layer made of oxide fine particles having a pore structure, a hole transport layer, a hole current collecting electrode, and a photosensitizing compound attached or fixed to the electron transport layer.
  • Another gist of the present invention is to provide a vehicle power supply device electrically connected to an electric device mounted on a vehicle and having at least a photoelectric conversion module and a storage capacitor, wherein the photoelectric conversion element constituting the photoelectric conversion module is provided.
  • a transparent conductive electrode Comprising a transparent conductive electrode, an electron transporting layer composed of oxidized fine particles having a pore structure, a hole transporting layer, a hole current collecting electrode, and a photosensitizing compound adhered or fixed to the electron transporting layer.
  • FIG. 1 is a schematic diagram of a typical photoelectric conversion element.
  • FIG. 2 is a schematic diagram of the solid-state photoelectric conversion device of the present invention.
  • FIG. 3 is a schematic diagram showing a configuration of a portable power supply device as one embodiment of the present invention.
  • FIG. 4 is a schematic perspective view showing the configuration of a portable electronic device and a portable telephone as a portable communication terminal according to one embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing an enlarged configuration of a photoelectric conversion element according to a portable power supply device as one embodiment of the present invention.
  • FIG. 6 shows each light in a single cell of a photoelectric conversion element, a single cell of a conventional single-crystal silicon solar cell, and a single cell of a conventional amorphous silicon solar cell according to an embodiment of the present invention. It is a figure which shows intensity-relative energy conversion efficiency characteristic.
  • FIG. 7 is a schematic perspective view showing the configuration of a portable computer as a portable electronic device according to one embodiment of the present invention.
  • FIG. 8 is a schematic diagram showing a configuration of a vehicle power supply device as one embodiment of the present invention.
  • FIG. 9 is a schematic perspective view showing a configuration of a photoelectric conversion module according to a vehicle power supply device as one embodiment of the present invention.
  • FIG. 10 is a schematic perspective view showing a configuration of a photoelectric conversion module according to a vehicle power supply device as one embodiment of the present invention.
  • FIG. 11 is a graph showing a photocurrent by the photoelectric conversion element manufactured in Example 2.
  • FIG. 12 is a voltage-current density characteristic diagram of the photoelectric conversion element according to one embodiment of the present invention.
  • FIG. 13 is a configuration diagram of a photoelectric conversion module according to one embodiment of the present invention.
  • FIG. 14 is a configuration diagram of a conventional PIN-type amorphous silicon solar cell module.
  • FIG. 15 is a configuration diagram of a photoelectric conversion module according to one embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
  • the photoelectric conversion element typically includes an electron collecting electrode 1, an electron acceptor, as shown in FIG. It comprises an electron transport layer 2, an electron donor / hole transport layer 3, and a hole collecting electrode 4.
  • the electron donor / hole transport layer and the hole current collecting electrode are the same solid substance, and the electron donor / hole transport layer (hereinafter, simply referred to as the hole transport layer) and the hole current collecting electrode are used.
  • the hole transport layer the electron donor / hole transport layer
  • FIG. 2 is a schematic diagram of one embodiment of the solid-state photoelectric conversion device of the present invention.
  • a solid substance that also serves as a hole transport layer and a hole current collector is indicated by reference numeral 8.
  • any known conductive material that is transparent to visible light can be used.
  • the thickness of the electron collecting electrode is preferably from 0.005 to 1 ⁇ ⁇ , and more preferably from 0.01 to 0.1 lm.
  • the electron collecting electrode is preferably provided on a substrate made of a material transparent to visible light in order to maintain hardness, and the thickness of the substrate is preferably 0.01 to 20 mm, more preferably 0 to 20 mm. l to 5 mm.
  • a substrate transparent to visible light for example, glass or a transparent polymer is used.
  • an electron transport layer formed by sintering oxide fine particles is preferably used as the electron acceptor / electron transport layer (hereinafter, simply referred to as an electron transport layer) used in the present invention.
  • the oxide used for the electron transporting layer is not particularly limited as long as it is an oxide capable of transmitting visible light and having an electron transporting property.
  • a metal such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, barium titanate or the like is used.
  • An oxide is used, and more preferably, anatase type titanium oxide is used.
  • the size of the fine particles is preferably from 5 nm to 100 nm, more preferably from 15 nm to 50 nm. When these oxide particles are sintered, usually a pore diameter of 2 to 20 nm is formed.
  • the thickness of the electron transport layer is preferably 0.01 to 5 ⁇ , more preferably 0.1 to 3 ⁇ m.
  • the photoelectric conversion element of the present invention is provided with a dense electron transporting layer between the electron collecting electrode and the electron transporting layer, if necessary, in order to avoid direct contact between the electron collecting electrode and the electron transporting layer. You may.
  • the dense electron transport layer means an electron transport layer having substantially no pores. However, there is no particular limitation as long as it has the same composition and crystal type as the electron transport layer formed by sintering the oxide fine particles.
  • a dense anatase-type titanium oxide film is provided between an electron collecting electrode and an electron transporting layer having a pore structure formed by sintering anatase-type titanium oxide fine particles.
  • a method of forming the titanium oxide by a spray drying method using an ethanol solution of diisopropoxytitanium bisacetyl acetonate may be mentioned.
  • a photosensitizing compound is attached or fixed to form a charge separation layer.
  • the photosensitizing compound used as the charge separation layer is not particularly limited as long as it is a compound that is photoexcited by the excitation light used, and specifically, (cis-di (thiocyanic acid) -N, N'-bis (2,2'-biviridyl 4,4'-dicarboxylic acid) Ruthenium complex dyes such as ruthenium (II), metal complexes of porphyrins and phthalocyanines, and organic dyes such as perylene dyes and zeocin dyes.
  • the photosensitizing compound may be used alone or in combination of two or more of these substances.
  • the mode of attachment or fixation may be such that the photosensitizing compound is present on the surface of the electron transporting layer, but is preferably chemically adsorbed.
  • the hole transport layer As the solid substance which also serves as the electron donor and hole transport layer (hereinafter, simply referred to as the hole transport layer) and the hole collecting electrode in the present invention, a substance having good hole transport ability is used.
  • a ⁇ -conjugated compound is preferable from the viewpoint of hole transporting ability, and a ⁇ -conjugated compound has at least 4 or more, preferably 6 or more, more preferably 8 carbon atoms constituting a conjugate. I just need more.
  • ⁇ -conjugated oligomers such as oligothiophene derivative, oligoparaphenylene derivative, oligopyrrole derivative, oligoparaphenylenevinylene derivative, polythiophene derivative, polyparaphenylene derivative, polypyrrole derivative, polyparaphenylene derivative, etc.
  • the ⁇ -conjugated polymer is preferred, but is not limited thereto.
  • the thiophene skeleton is used as the structural unit from the viewpoint of hole transport ability and production.
  • Compounds containing as the above are preferable, and among them, oligomers or polymers having the following atomic group (1) are more preferable.
  • each R 2 independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, or a dialkylamino group. 1 )
  • an alkoxy group is preferable, and among them, a group in which two alkoxy groups of Ri and R 2 are bonded to each other to form a cyclic structure is more preferable. .
  • the above-mentioned ⁇ -conjugated oligomer or ⁇ -conjugated polymer is doped with, for example, iron chloride ( ⁇ ), iodine, iron (III) tris-p-toluenesulfonate, or the like. May be used.
  • A- represents a pair of anions derived from a dopant.
  • A- represents a pair of anions derived from a dopant.
  • the photosensitized electrode is fine.
  • the doping concentration may be different between the ⁇ -conjugated polymer in the pore and the ⁇ -conjugated polymer in the upper part of the photosensitized electrode surface.
  • the ⁇ -conjugated polymer in the part is preferably in a highly doped state in order to function as a hole collecting electrode.
  • the concentration of the dopant when represented by the molar ratio of the dopant to the repeating unit of the conjugated polymer, the concentration is preferably higher than 10: 1, more preferably higher than 5: 1. Good case.
  • the doped ⁇ -conjugated polymer means a polymer having a cation site in a part of the main chain of the ⁇ -conjugated polymer due to the action of the dopant.
  • the compound represented by the following formula (3) is an example of a structural unit forming a complex compound composed of a ⁇ -conjugated compound and a metal element used in the present invention.
  • the method of introducing the above-described solid hole transporting layer and hole current collecting electrode into the pores of the electron transporting layer and behind the electron transporting layer includes a ⁇ -conjugated method.
  • Polymerization after impregnating with a solution containing a compound or complex compound, or after impregnating a mixed solution containing a monomer that forms a ⁇ -conjugated polymer, a polymerization catalyst, and if necessary, a compound that reduces the polymerization rate A method in which the solvent is removed to form a solid material layer up to the outermost surface can be used.
  • the operations of impregnation, polymerization, and solvent removal may be performed plural times.
  • to form to the outermost surface means that the oxide and the sensitizing compound which are the electron transport layer are completely covered with the solid material until the oxide and the sensitizing compound are completely covered with the solid material layer which is also a hole transport layer and a hole current collector. Means to be formed.
  • the solvent is not particularly limited as long as it can dissolve a conjugated compound and / or a complex compound, or a monomer that forms a conjugated polymer, a polymerization catalyst, and a compound that controls a polymerization rate. Not determined.
  • Preferred solvents include butanol, ethanol, acetonitrile and the like.
  • the pressure is reduced while the photosensitizing electrode is immersed in the solution or the mixed solution, or the solution or the mixed solution is mixed on the photosensitizing electrode.
  • the pressure may be reduced after the solution is developed.
  • the degree of vacuum at the time of decompression may be lower than atmospheric pressure depending on the viscosity of the solution or the mixed solution, but is preferably lower than or equal to 160 Pa and more preferably lower than or equal to 600 Pa It is as follows. Although there is no particular lower limit for the degree of vacuum, it is preferably 1 O O Pa or more in view of simplicity in production.
  • the compound that reduces the polymerization rate of the ⁇ -conjugated polymer is not particularly limited as long as it does not directly react with the monomer that forms the ⁇ -conjugated polymer and reduces the polymerization rate.
  • a Lewis basic compound is used, among which a Lewis basic nitrogen atom or a compound having a Lewis basic sulfur atom is preferable, and a cyclic compound having a Lewis basic nitrogen atom such as imidazole is more preferable. .
  • the polymer when polymerizing a ⁇ -conjugated polymer, the polymer may be left at room temperature under reduced pressure or may be subjected to a heat treatment. In order to form a solid layer up to the outermost surface of the electron transport layer, the above treatment may be repeated.
  • a solution containing a ⁇ -conjugated compound or a complex compound, or a mixture containing a monomer that forms a ⁇ -conjugated polymer, a polymerization catalyst, and a compound that reduces the polymerization rate are contained in the pores of the oxide that is the electron transport layer.
  • the oxide When impregnating the solution into the pores of the oxide while applying ultrasonic waves, the oxide may be immersed in the solution or the mixed solution and ultrasonic waves may be applied.
  • the doped ⁇ -conjugated oligomer or ⁇ -conjugated polymer is obtained by adding a thiophene compound as described below, preferably in an alcoholic solvent, in the presence of a Lewis basic compound such as imidazole, in anhydrous tris-p-toluenesulfonic acid. It can be produced by reacting with a strong acid metal compound such as (III). HOHW
  • the photoelectric conversion device of the present invention is formed from a solid material containing a metal oxide, a photosensitizing compound and a ⁇ -conjugated compound, It is preferable that the metal oxide has pores and a ⁇ -conjugated compound is present in at least a part of the pores.
  • a transparent conductive electrode (electron current collecting electrode) 5 coated on a substrate such as glass is provided with an electron acceptor / electron transport layer 6 made of a metal oxide such as titanium oxide.
  • Photosensitizing compound 7 is chemisorbed on a part of the electron transport layer.
  • a solid substance ( ⁇ -conjugated compound) 8 which is a hole transport layer and a hole current collecting electrode, is provided in contact with the photosensitizing compound 7 and further partially enters the pores of the titanium oxide 6.
  • the photoelectric conversion element of the present invention a metal oxide, a solid material containing a photosensitizer compound and ⁇ -conjugated compound, the surface resistivity of the outermost surface 1 0 3 Omega Zeta mouth of the solid material It can be:
  • the surface resistance is preferably 100 ⁇ or less, more preferably 50 ⁇ or less. The smaller the surface resistance is, the more preferable it is, but it is often 5 ⁇ / b or more.
  • the photoelectric conversion element of the present invention can be formed transparent by selecting a material, though it is solid.
  • the element of the present invention can have a light transmittance of 500 mii of 5% or more.
  • the transmittance is preferably 10% or more, and more preferably 20% or more. The higher the transmittance, the better.
  • the transmittance is preferably 95% or less, particularly preferably 80% or less.
  • the term “single cell element” refers to an element having one photoelectric collecting electrode and one hole collecting electrode and having a photoelectric conversion function in which these electrodes are not connected in series. Say.
  • the photoelectric conversion element of the present invention has the above-described configuration, it is possible to make the single cell element flexible with respect to at least two axes on the electrode plane by selecting a material.
  • the term “flexible” means that a single cell element can be bent about 5 ° or more, particularly 10 ° or more about a desired axis without breaking.
  • the present invention relates to a solid-state photoelectric conversion element containing a solid substance that also serves as a hole transport layer and a hole current collecting electrode as a component, and the hole transport layer and the hole current collecting electrode also serve as the hole transport layer and the hole current collecting electrode.
  • Good electrical connection at the collecting electrode interface After the formation of the hole transport layer as described above, it is possible to simply and efficiently manufacture, for example, it is possible to avoid a manufacturing process of forming a hole current collecting electrode by depositing gold or the like under high vacuum.
  • the present invention is an all-solid-state device in which the hole transport layer and the hole current collecting electrode are also used, restrictions on device design are reduced and a photoelectric conversion device having a free shape can be manufactured.
  • the present invention can be applied to a portable solar cell and a power supply device using the solar cell.
  • the light conversion efficiency is high even in places with low light quantity, such as under cloudy weather or under fluorescent lighting, it is excellent for use in areas with short sunshine hours and equipment that is not always used outdoors.
  • any device that conventionally uses a solar cell or a power supply device using the same can be used.
  • a solar cell for an electronic desk calculator or a wristwatch can be used.
  • Good examples of the advantageous use of the above-described features of the photoelectric conversion device of the present invention include, for example, mobile phones, portable radios and other portable audio devices, car accessories, and road signs used in areas with short sunshine hours. And the like. It can also be used as an auxiliary power supply to extend the continuous use time of rechargeable or dry battery type electric appliances, and it is particularly effective to use it as a power supply for charging secondary batteries.
  • the portable power supply device of the present invention is a portable power supply device connected to a secondary battery for driving a portable electronic device and having at least a photoelectric conversion element and a storage capacitor, wherein the solid-state imaging device of the present invention is used as the photoelectric conversion element. It is characterized by using a photoelectric conversion element. In this case, at least a part of the photoelectric conversion element may be configured with a curved surface. Further, it is preferable that the hole transport layer is made of a solid substance, and that the solid substance also serves as the hole transport layer and the hole current collecting electrode. Further, it is preferable that the solid substance contains a ⁇ -conjugated compound.
  • a portable communication terminal includes the portable power supply device described above.
  • a portable computer includes the portable power supply device according to any of the above. It is characterized by doing.
  • FIG. 3 to 7 are views showing a portable power supply device as one embodiment of the present invention.
  • the portable power supply device of the present invention is applied to a portable electronic device and a portable telephone as a portable communication terminal will be described.
  • the term “portable” means that it can be carried by one person.
  • the portable electronic device 10 includes a photoelectric conversion module 1 OA and a large-capacity electric double-layer capacitor (storage capacitor) connected in parallel to the photoelectric conversion module 10 A. In addition to providing 10 C, it is interposed between the photoelectric conversion module 10 A and the electric double layer capacitor 10 C to achieve impedance matching between the photoelectric conversion module 1 OA and electric double layer capacitor 10 C. It is configured as a hybrid power supply device having a rectified impedance conversion circuit 10B.
  • the portable power supply device 10 drives a mobile phone (portable electronic device, portable communication terminal) 20 via the connection portions 11 and 11 on the electric double layer capacitor 10 C side. Connected to battery 21.
  • the photoelectric conversion module 1 OA here is composed of a plurality (eight) of single cells (photoelectric conversion elements) 10 a connected in series. It is attached along the curved surface of the side corner of the outer surface of the casing of No. 0. As a result, at least a part of the single cell 10a and, consequently, the photoelectric conversion module 1OA has a curved shape along the curved surface of the outer surface of the casing of the mobile phone 20.
  • connection parts 11 and 11 are installed in the casing of the mobile phone 20, and the connection parts 11 and 11 are connected to, for example, a charging terminal generally provided in the secondary battery 21.
  • the type power supply device 10 and the mobile phone 20 are substantially integrally formed.
  • the photoelectric conversion module 1 OA When the photoelectric conversion module 1 OA is exposed to light, the photoelectric conversion module 1 OA outputs electricity, and the secondary battery 21 can be charged with the electricity.
  • the electric double-layer capacitor 10 C has a large capacity and can be charged in a very short time and discharged for an extremely long time.
  • the portable power supply device 10 is provided with a large-capacity electric double layer capacitor 10C as described above.
  • the electric double-layer capacitor 10 C is capable of storing a large amount of current rapidly even when the current is rapidly supplied from the photoelectric conversion module 10 A, and also for the secondary battery 21.
  • current can be supplied at a relatively slow speed. Therefore, even when a large amount of current is supplied from the photoelectric conversion module 1 OA, the current can be efficiently supplied to the secondary battery 21 through the electric double layer capacitor 10 C and charged. I have.
  • the electricity stored in the electric double-layer capacitor 10 C is supplied to the secondary battery 21. It is designed to be charged.
  • the electric double-layer capacitor 10 C is particularly limited in material and type as long as it has a large capacity and can be charged in an extremely short time and discharge can be performed for an extremely long time.
  • specifications such as capacity are determined appropriately according to the purpose of use and operation method.
  • a configuration may be adopted in which the pulse charger 10D is provided on the secondary battery 21 side with respect to the electric double layer capacitor 10C.
  • the electricity stored in the electric double-layer capacitor 10C via the pulse charger 1OD can be more stably supplied to the secondary battery 21 at a predetermined speed.
  • a DC / DC converter may be interposed between the electric double layer capacitor 10 C and the secondary battery 21.
  • Single cell (photoelectric conversion element) 10a is a solid cell containing a metal oxide, a photosensitizing compound, and a ⁇ -conjugated compound. It is preferable that the metal oxide has a photosensitizing compound on the surface of the metal oxide, the metal oxide has pores, and at least a part of the pores has a ⁇ -conjugated compound. .
  • the photoelectric conversion element 10a includes a substrate 9, a transparent conductive electrode 5, an electron transport layer 6, a photosensitizing compound 7, a hole transport layer 3, and a hole collecting electrode. 4 and a base material 9 'are laminated in this order.
  • the base material 9 supports the transparent conductive electrode 5 and is made of a known material having a light transmitting property, such as glass or a transparent polymer.
  • the thickness of the base material 9 is appropriately set according to the intended use, but is preferably from 0.1 to 2000 ⁇ m, and more preferably from 0.1 to! 1 ⁇ m. By setting the thickness of the substrate 9 in such a range, the strength and light transmittance of the substrate 9 can be ensured.
  • the transparent conductive electrode 5 a known material generally used for a transparent conductive electrode is used.
  • indium tin oxide, fluorine-doped tin oxide, and the like are used. Of these materials, fluorine-doped tin oxide is particularly preferable.
  • the thickness of the transparent conductive electrode 5 is preferably from 0.01 ⁇ to 1 ⁇ , more preferably from 0.01 to 0.1 ⁇ . By setting the thickness of the transparent conductive electrode 5 in such a range, the power generation capacity and light transmittance of the photoelectric conversion module 1OA can be secured.
  • the electron transport layer 6 is formed by sintering oxide fine particles and has a plurality of pore structures.
  • the oxide fine particles may be any oxides that transmit visible light and have an electron transporting ability, for example, titanium oxide, zirconium oxide, zinc oxide, tin oxide and parium titanate, but are not limited thereto. Not done.
  • the size (diameter) of the oxide fine particles is preferably from 5 to 100 nm, more preferably from 15 to 50 nm. When the oxide particles having such a size are sintered, usually, pores having a diameter of 10 to 20 nm are formed. When the pore diameter is formed in such a range, the photosensitizing compound 4 can be supported reliably and stably.
  • the thickness of the electron transport layer 6 is preferably from 0.1 to 3 / m, more preferably from 0.1 to 1. By setting the thickness of the electron transport layer 6 in such a range, the power generation capacity and light transmittance of the photoelectric conversion module 1OA can be secured.
  • the photosensitizing compound 7 adheres or adheres to the surface of the electron transport layer 6 so as to enter the pores, and forms an electrification separation layer together with the electron transport layer 6.
  • the photosensitizing compound 7 may be any as long as it efficiently absorbs sunlight or light emitted from a fluorescent lamp, and efficiently transfers electrons to the oxide (electron transport layer) 6.
  • ruthenium complex dyes such as ruthenium (II), metal complexes of porphyrins and phthalocyanines, perylene dyes zeosin Organic dyes such as, but not limited to, dyes
  • the photosensitizing compound may be used alone or in combination of two or more of these substances.
  • the mode of attachment or fixation of the photosensitizing compound 7 may be any as long as the photosensitizing compound 7 can stably exist on the surface of the electron transport layer 6, and may be physical or chemical. But by chemisorption Preference is.
  • the hole transport layer 3 transports holes by providing electrons to the photosensitizing dye thione generated after photosensitization in the photosensitizing compound 7 and receiving electrons from the hole current collecting electrode 4 to return to the original position.
  • Any material that can be used such as a solution containing an electrolyte (electrolyte solution) or a solid substance having a hole transporting ability, is used.
  • Examples of the electrolyte solution include, for example, an acetate nitrile solution of lithium iodide and iodine, an acetonitrile solution of tetrapropylammonium monoxide and iodine, lithium iodide, and 1,2-dimethyl-methyl.
  • Examples include, but are not limited to, a solution of 3-propylimidazolymoxide, iodine and 4-tert-butylpyridine in 3-methoxypropionitrile.
  • Examples of the solid substance having a hole transport ability include, for example, hydrazone-based compounds, oligothiophene derivatives, oligoaniline derivatives, ⁇ - conjugated oligomers such as oligopyrrole derivatives, polythiophene derivatives, and polyparaffins.
  • Examples include, but are not limited to, ⁇ -conjugated polymers such as elene derivatives and polyaline derivatives.
  • a dopant such as iodine or iron (III) chloride may be doped in order to adjust the hole transport ability and the fullerium level.
  • the above-described solid substance having a hole transport ability is used for the hole transport layer 3.
  • the solid substance can be used as the hole transport layer 3 and the hole current collecting electrode 4 to be integrated.
  • As a specific method for forming such a structure for example, highly doped polyaniline or highly doped poly (3,4-ethylenedioxythiophene) is polymerized in the pores of the electron transport layer 6. There is a method of forming the hole transport layer 5 up to the outermost surface layer.
  • the hole transport layer 3 may be composed of either an electrolyte solution or a solid substance, but is preferably composed of a solid substance because there is no liquid leakage.
  • the hole transport layer 3 and the hole current collecting electrode 4 are also used and integrated by a solid substance.
  • the electrical connection at the interface between the hole transport layer 3 and the hole current collecting electrode 4 is improved.
  • a hole current collecting electrode is formed by depositing gold or the like under a high vacuum after forming a hole transport layer, but such a manufacturing process is omitted. It can be manufactured simply and efficiently, and the manufacturing cost can be reduced.
  • the hole collecting electrode 4 may be any as long as it can collect holes, and is specifically, for example, platinum, carbon, and gold, but is not limited thereto.
  • the hole transport layer 3 also serves as the hole current collecting electrode 4 as described above, the hole current collecting electrode 4 need not be provided separately from the hole transport layer 3, as a matter of course.
  • the base material 9 ′ supports the hole collecting electrode 4, and its material is the same as the material of the base material 9 supporting the transparent conductive electrode 5.
  • the hole transport layer 3 is made of a solid material and platinum, gold, or the like is deposited on the solid material to form the hole current collecting electrode 4, the hole current collecting electrode 4 is supported by the hole transport layer 3.
  • the base material 9 ′ is not always necessary.
  • the base material 9 ′ is not necessarily required.
  • a single cell (photoelectric conversion element) 10a is composed of a solid material containing a metal oxide, a photosensitizing compound and a ⁇ -conjugated compound
  • this solid material has a surface resistance value of its outermost surface
  • the surface resistance is preferably 100 ⁇ or less, more preferably 50 or less. The smaller the surface resistance is, the more preferable it is, but it is often 5 ⁇ or more.
  • the photoelectric conversion element of the present invention can be formed transparent by selecting a material.
  • the device of the present invention can have a transmittance of 50 O nm light of 5% or more.
  • the transmittance is preferably 10% or more, more preferably 20% or more. The higher the transmittance, the better.
  • the transmittance is preferably 95% or less, particularly preferably 80% or less.
  • a “single cell element” refers to an element having a photoelectric conversion function in which each of the electrodes has one electron collecting electrode and one hole collecting electrode, and these electrodes are not connected in series.
  • the photoelectric conversion element of the present invention has the above-described configuration, it is possible to make the single cell element flexible with respect to at least two axes on the electrode plane by selecting a material.
  • the term “flexible” means that a single cell element can be bent about 5 ° or more, particularly 10 ° or more about a desired axis without breaking.
  • the portable power supply device 10 as one embodiment of the present invention is configured as described above, the current output from the photoelectric conversion module 1 OA under the sunshine or the fluorescent lamp is the electric double layer capacitor 10. After being stored in C, it is discharged from the electric double layer capacitor 10 C and the secondary battery 21 is charged. Therefore, there is an advantage that the secondary battery 21 can be charged without performing a special operation.
  • the electric double layer capacitor 10 C has a fast charging speed and a slow discharging speed
  • the electric current supplied from the photoelectric conversion module 1 OA at a relatively high speed is used for the secondary battery having a relatively slow charging speed. It can be supplied at a relatively slow rate for 21. Therefore, there is an advantage that the rechargeable battery 21 can be charged at an appropriate speed.
  • electricity output from the photoelectric conversion module 1 OA under sunlight or fluorescent lighting is stored / charged in the electric double layer capacitor 10 C or the secondary battery 21, so that the environment cannot be used at night or where light cannot be obtained.
  • the mobile phone 20 can be used stably.
  • the maximum output voltage under simulated sunlight having an intensity of 10 O mW / cm 2 is 0.64 V, whereas the maximum output voltage using single crystal silicon is The maximum output voltage under the same conditions for a single cell with a transducing element is 0.4 V (Adhanst Rectox Series', 1-3 Taiyo Energy Engineering Baifukan p. 247).
  • the maximum output voltage of the photoelectric conversion element (single cell) 10a according to the present invention is higher than the maximum output voltage of the photoelectric conversion element (single cell) using single crystal silicon, the photoelectric conversion module can have a smaller area than using a photoelectric conversion element using single-crystal silicon.
  • the maximum output voltage and the maximum output current density in the single cell 10a according to the present invention are different from each other under simulated sunlight having a light intensity of 10 O mW / cm 2 , in which the energy conversion efficiencies are substantially the same.
  • the maximum output voltage of the solar cell single cell using a crystalline silicon according to but is substantially the same as the maximum output current density, as shown in FIG. 6, the light intensity is lower than l OO mWZ cm 2,
  • the energy conversion efficiency is reduced.
  • the solid line a in the figure the single cell 1 0 a of the photoelectric conversion module 1 0 a, the light intensity is less than 1 0 0 mW / cm 2 area (low illuminance under) even high energy conversion Efficiency can be maintained.
  • the photoelectric conversion module 1OA it is possible to charge the secondary battery even in a place with a small amount of light, such as under cloudy weather or under a fluorescent light, or in an area with short sunshine hours. There is an advantage that the secondary battery can be charged even when the mobile phone is used indoors for a relatively long time.
  • the photoelectric conversion element 10a since it is not always necessary to use a material having low moldability, such as glass, for example, a transparent polymer can be used as the material of the base material 9, 9 '. It is possible to design the shape of the 10a and hence the photoelectric conversion module 1OA as appropriate, and as shown in Fig. 4, it is attached along the curved surface (here, the side corner of the mobile phone 20). It is also possible.
  • the photoelectric conversion element used in the present invention has high energy conversion efficiency and can be made smaller than before, and is easy to mold, the portable electronic device is thus downsized and its shape is complicated. Among them, it has an extremely advantageous advantage that it can be stably mounted on portable electronic devices.
  • silicon-based photoelectric conversion elements generally used in the past have been unstable in the supply of materials such as silicon-silane gas required for manufacturing
  • the silicon-based photoelectric conversion elements required for the present photoelectric conversion element 10a are not stable. Since the material is supplied relatively stably, there is an advantage that the photoelectric conversion element 10a, and furthermore, the photoelectric conversion module 1OA and the power supply device 10 can be manufactured stably.
  • the portable power supply device of the present invention is applied to a portable telephone as a portable electronic device and a portable communication terminal.
  • the present invention can be widely applied to portable electronic devices, for example, to portable computers.
  • the portable computer 30 is generally configured such that a main body 31 having a keyboard and a display section 32 are foldable.
  • a photoelectric conversion module including a plurality of sheet-like photoelectric conversion elements 10a can be attached to the back surface (the surface not facing the main body) 32a.
  • the other components of the portable power supply unit may be housed inside the case of the PC main unit 31 or the case of the display unit 32.
  • the portable power supply device of the present invention does not need to be integrated with the portable electronic device as in the above-described embodiment, and may be provided separately.
  • the mobile phone can be plugged in to charge the secondary battery attached to the mobile phone.
  • portable phones What is necessary is just to make it electrically connect with the connection part of a source device.
  • the photoelectric conversion element is mounted on the outer surface of the casing of the portable power supply device.
  • the storage capacitor ⁇ rectifying impedance or the like may be provided inside the casing, and the photoelectric conversion element may be connected to a cable drawn from the casing outside the casing.
  • the portable electronic device and the portable power supply device can be housed in a bag or the like, and only the photoelectric conversion element can be installed outside the bag using a fastener or the like.
  • a vehicle power supply device is a vehicle power supply device that is electrically connected to a battery or electric equipment mounted on the vehicle and has at least a photoelectric conversion module and a storage capacitor. It is characterized by using the element of the present invention as an element.
  • At least a part of the photoelectric conversion module may be configured to be foldable, and at least a part of the photoelectric conversion module may be configured to have a curved surface.
  • the hole transport layer may be composed of a solid substance, and the solid substance may also serve as the hole transport layer and the hole current collecting electrode.
  • the solid substance preferably contains a ⁇ -conjugated compound.
  • the photoelectric conversion module may be detachable from the vehicle.
  • a vehicle power supply device hereinafter, also simply referred to as a power supply device
  • FIGS. 3 to 7 the portable power supply device shown in FIGS. 3 to 7 described above, and the description thereof is partially omitted.
  • a starter motor 101 for starting the engine As shown in FIG. 8, in an automobile (hereinafter referred to as a vehicle) to which the power supply device is applied, a starter motor 101 for starting the engine, a starter motor 101, and the like are used as an engine starter circuit.
  • Battery (rechargeable battery) 102 that supplies power Is provided.
  • the starter motor 101 When the driver turns on the starter switch 103 by key operation, power is supplied from the battery 102 to the starter motor 101, and the starter motor 101 operates to rotate the crankshaft to start the engine. It has become.
  • the battery 102 supplies power to not only the starter motor 101 but also various electric devices mounted on other vehicles.
  • the vehicle is also equipped with an alternator (generator) 104 driven by an engine to charge the battery.
  • the alternator 104 generates electric power by being rotationally driven by a crankshaft during operation of the engine, and the generated electric power is charged to the battery 102 via a cable. As shown in FIG. 8, the power supply device 10 is connected to the battery 102 in parallel with the alternator 104, and charges the battery 102 together with the alternator 104. It has become.
  • the power supply device 101 includes a photoelectric conversion module 1 OA and a large-capacity electric double layer capacitor (storage capacitor) 10 C connected in parallel to the photoelectric conversion module 1 OA. Both are interposed between the photoelectric conversion module 1 OA and the electric double layer capacitor 10 C, and rectify to match the impedance between the photoelectric conversion module 1 OA and the electric double layer capacitor 10 C. It is configured as a hybrid power supply device having an impedance conversion circuit 10B. Then, as shown in FIG. 9, the photoelectric conversion module 1 OA is attached to a sunshade 105 that is placed in the vehicle interior facing the front glass and the rear glass, and a plurality of single conversion modules are provided.
  • a sunshade 105 that is placed in the vehicle interior facing the front glass and the rear glass, and a plurality of single conversion modules are provided.
  • the cell (photoelectric conversion element) 10a is configured to be connected in series or in parallel.
  • the sunshade 105 is composed of a plurality of planar members 105a that can be bent together, and is foldable.
  • Each single cell 10a is disposed so as not to straddle a plurality of planar members 105a, whereby the photoelectric conversion module 1OA composed of these single cells 10a is formed. It is constructed so that it can be folded together with Sansade 105.
  • the photoelectric conversion module 1 OA is installed in the vehicle body separately from the OA, The photoelectric conversion module 1 OA is detachably connected to connection portions 11 provided at predetermined positions (for example, around an instrument panel) in a vehicle cabin.
  • the sunshade 105 performs sunshade at the same time as the sunshade during sunshine.
  • the conversion module 1 OA generates power, and the output electricity can charge the battery 102.
  • the sunshade 105 is provided with a suction plate (not shown), and is fixed to the door glass by the suction plate.
  • the electric double layer capacitor 10 C one that can be charged in a very short time and can be discharged for a very long time is used.
  • the battery 102 stores electricity by chemical change, Is relatively slow.Therefore, if current is directly supplied from the photoelectric conversion module 1 OA to the battery 102, the storage of the battery 102 will be slower than the current supply speed from the photoelectric conversion module 1 OA. The electric speed is slow and overflow occurs. For this reason, the power supply device 101 is provided with the large-capacity electric double layer capacitor 1 OC as described above.
  • the electric double-layer capacitor 100 C is capable of storing the current rapidly and in large quantities even when the current is rapidly supplied from the photoelectric conversion module 1 OA.
  • the current can be supplied at a moderate speed. Therefore, even when a large amount of current is supplied from the photoelectric conversion module 1 OA, the current can be efficiently supplied to the battery 102 through the electric double layer capacitor 10 C and charged. .
  • the capacity of the electric double layer capacitor 100 C may be 50 F or more, but it is appropriately set according to the application, and is usually 50 to 500 F, preferably 100 to 3 F. 0000F, more preferably 150 to 100OF.
  • the pulse charger 10D may be provided on the battery 102 side with respect to the electric double layer capacitor 10C.
  • the electricity stored in the electric double layer capacitor 10C via the noise charger 10D can be supplied to the battery 102 more stably at a predetermined speed.
  • a DC Z DC converter may be interposed between the electric double layer capacitor 10C and the battery 102.
  • the single cell (photoelectric conversion element) 10a is the same as that used in the portable power supply device.
  • the power supply device 10 Since the power supply device 10 according to an embodiment of the present invention is configured as described above, the current output from the photoelectric conversion module 1OA in sunlight is stored in the electric double layer capacitor 10C after the electric power is stored in the electric double layer capacitor 10C. Discharged from the electric double layer capacitor 10C, the battery 102 is charged. Therefore, there is an advantage that the battery 104 can be charged even when charging cannot be performed by the alternator 104 while the engine is stopped.
  • the battery 102 can be charged without operating the engine, there is an advantage that it is possible to operate electric devices such as an air conditioner and an audio device for a long time without operating the engine.
  • electric machines mounted on vehicles For example, there is no need to operate the engine when the vehicle is stopped, as in the past, so that there is no need to operate the engine to consume fuel and emit exhaust gas.
  • the electric double layer capacitor 10 C has a fast charging speed and a slow discharging speed
  • the electric current supplied from the photoelectric conversion module 1 OA at a relatively high speed is used for the battery 10 C having a relatively slow charging speed. 2 can be supplied at a relatively slow speed. Therefore, there is an advantage that the battery 102 can be charged at an appropriate speed.
  • the maximum output voltage under simulated sunlight having an intensity of 10 O mW / cm 2 is 0.64 V, whereas the maximum output voltage using single crystal silicon is The maximum output voltage under the same conditions for a single cell of the conversion element is 0.4 V (ad / inst- ertox sili- 1-3 Solar Pelunky Engineering Baifukan p.247).
  • the maximum output voltage of the photoelectric conversion element (single cell) 10a according to the present invention is higher than the maximum output voltage of the photoelectric conversion element (single cell) using single crystal silicon, the photoelectric conversion module is smaller than using a photoelectric conversion device using single crystal silicon! /, And has the advantage that the area can be reduced and the size and weight can be reduced. Further, the maximum output voltage and the maximum output current density in the single cell 10a according to the present invention are different from each other under simulated sunlight having a light intensity of 10 O mW / cm 2 , in which the energy conversion efficiencies are substantially the same.
  • the maximum output voltage of the solar cell single cell using a crystalline silicon but is substantially the same as the maximum output current density, as shown in FIG. 6, the light intensity is lower than 1 0 0 mW / cm 2 Therefore, in a single cell using single-crystal silicon shown by the dotted line b in the figure and a single cell using amorphous silicon shown by the broken line c in the figure, the relative energy conversion efficiency decreases.
  • the solid line a in the figure but the single cell 1 0 a of the photoelectric conversion module 1 OA, the light intensity is 1 0 0 mW / cm 2 by remote region lower (low light) High relative energy conversion efficiency can be maintained.
  • the photoelectric conversion module 1 OA it is possible to charge the battery even when the engine is not running even in places with low light quantity such as under cloudy weather or under fluorescent lighting, and in areas with short sunshine hours.
  • the advantage of being possible is there.
  • the photoelectric conversion module 1OA can be detached from other members (rectified impedance conversion circuit 10B, electric double layer capacitor 10C, etc.) installed in the vehicle body, that is, detachable from the vehicle body,
  • the photoelectric conversion module 1 OA that requires a large area can be removed and then folded and stored in the trunk room or outside when the power supply 10 ′ is not used. is there.
  • silicon-based photoelectric conversion elements generally used in the past have been unstable in the supply of materials such as silicon-silane gas required for manufacturing, the silicon-based photoelectric conversion elements required for the present photoelectric conversion element 10a are not stable. Since the material is supplied relatively stably, there is an advantage that the photoelectric conversion element 10a and thus the photoelectric conversion module 1OA and the power supply device 10 'can be stably manufactured.
  • vehicle power supply device of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the invention.
  • the power supply device 10 ′ is connected to the battery 102.
  • the power supply device 10 ′ may be directly connected to electric devices necessary for starting the engine, such as a starter motor and a spark plug. It may be.
  • the alternator is driven by the engine to generate electricity and charge the battery. Therefore, by directly supplying electricity from the power supply device 10 to the electric device so that the engine can be started even when the storage of the battery is completely consumed, the storage amount of the battery can be secured stably. It is.
  • the photoelectric conversion element 10a has, for example, a waveform cross-sectional shape as shown in FIG.
  • the sunshade 105 may be provided with the photoelectric conversion module 1 OA.
  • sunlight irradiates the photoelectric conversion module 10A regardless of the angle of the sun.
  • the photoelectric conversion module 1 OA may be mounted outside the vehicle body instead of the sunshade.
  • the photoelectric conversion module 1 OA since it is not always necessary to use a material having low moldability such as glass, for example, a transparent polymer can be used as the material of the base materials 9 and 9 ', It is possible to appropriately set the shape of the photoelectric conversion module 1 OA, for example, by forming at least a part of the photoelectric conversion module 1 OA on a curved surface, for example, to form the photoelectric conversion module 1 OA.
  • the shape can be made to match the vehicle body.
  • the photoelectric conversion module 1 OA is not limited to a flat surface, the photoelectric conversion module 1 OA can be attached to the outside of the vehicle body with a larger area than before, and the battery charging or the driving of electric devices can be more effectively performed. It has the advantage of being able to do so.
  • the vehicle power supply device of the present invention is not limited to this, and may be, for example, a pike, a boat, or an airplane. It can also be applied to In any case, the vehicle power supply device of the present invention can be widely applied to vehicles to which power is not constantly supplied from an external power supply.
  • a suspension of titanium oxide fine particles (80% crystalline anatase, particle size of about 20 nm) is applied to a 1 mm thick transparent conductive glass and sintered, and then used as a sensitizing dye (cis-di (thiocyanate) 1), ⁇ '-bis (2,2'-biviridyl-14, '-dicarboxylic acid) Ruthenium (II) chemisorbed photosensitized electrode to 3,4-ethylenedioxythiophene 0.0 70 g, anhydrous tris-para-toluenesulfonate iron (III) 0.547 g, imidazole 0.050 g dissolved in methanol 2.OOO g was immersed in a mixed solution for 15 minutes Thereafter, the mixture was heated at 110 ° C for 5 minutes, and poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonic acid anion was polymerized and filled in the pores.
  • the total thickness of the film formed on the conductive glass was about 1 ⁇ and about 2 ⁇ .
  • the sheet resistance of the surface was measured by the four-point needle method, it was 20 ⁇ / mouth, and the poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonate anion formed to the outermost surface had holes. It was confirmed that it worked as a current collecting electrode.
  • the electrical conductivity in the film thickness direction of a polymer filled with poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonate ayon in the pores is determined by the tris-concentration in the pores.
  • the electrical conductivity in the film thickness direction was about 9 orders of magnitude higher than that in the case where poly (3,4-ethylenedioxythiophene) doped with para-toluenesulfonic acid anion was not filled. It was found that in the sample prepared by the method described above, the transparent conductive glass and the poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonic acid anion were conductive.
  • the transmittance of a film with a total thickness of about 1 ⁇ is 44% for irradiation light of 500 nm wavelength and 44% for irradiation light of 650 nm wavelength. 74%.
  • the transmittance of a film with a total thickness of about 2 Aim including a transparent conductive glass with a thickness of 1 mm, is 44% for irradiation light with a wavelength of 500 nm and 650 nm for irradiation light. It was 5 1%.
  • a suspension of titanium oxide fine particles (80% crystalline anatase, particle size of about 20 nm) is applied to a 1 mm thick transparent conductive glass and sintered, and then a sensitizing dye (cis-di (thiocyanate)) is used.
  • a sensitizing dye cis-di (thiocyanate)
  • (3,4-Ethylenedioxythiophene) layer was formed. Attach the lead wire to a layer of poly (3,4-ethylenedioxythiophene) with transparent conductive glass and tris-para-toluenesulfonic acid anion doped on the surface of the photosensitizing electrode.
  • the photoconductive conversion device of the present invention was obtained. In this case, as in Example 1, the transparent conductive glass and the poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonic acid anion were conductive.
  • This photoelectric conversion device was measured 40 0 nm or less and 1 0 00 light of nm or more wavelengths to the force Tsu you encountered a xenon lamp light source intensity 1. irradiated with the 34 mW / cm 2 light short circuit current However, despite the conduction of the transparent conductive glass and the poly (3,4-ethylenedioxythiophene) doped with tris-para-toluenesulfonate anion, the photocurrent is still high as shown in Fig. 11. Observed.
  • the solid substance filled in the pores of the photosensitizing electrode functions as a hole transport layer and has good electrical connection with the solid layer on the surface of the photosensitizing electrode. It turned out that it worked as a hall current collecting electrode.
  • a transparent conductive electrode 5 is coated on a glass substrate (substrate) 9 with fluorine-doped tin oxide as a transparent conductive electrode 5 to form a transparent conductive glass.
  • a suspension of titanium oxide fine particles (crystal anatase 80%, particle diameter about 20 nm) is applied as the electron transport layer 6 and sintered at 450 ° C in air. I do.
  • (cis-di (thiocyanic acid) -N, N, bis (2,2'-bipyridyl 1,4,4, dicarboxylic acid) ruthenium (II) as photosensitizing compound 7 is chemically adsorbed on the electron transport layer 6.
  • a photosensitized electrode was prepared.
  • a transparent conductive glass is formed by coating fluorine-doped tin oxide on a glass substrate (base material) 9 ', and platinum is applied to the transparent conductive glass from the tin oxide. This was coated to form a hole current collecting electrode 4.
  • the electrolyte solution was filled as a hole transport layer 3 between the photosensitized electrodes 9, 5, 6, 7 and the hole current collecting electrode 4, thereby forming a single cell 10a.
  • the cell size is 400 nm or less.
  • the dimensions of the module were 49 mm ⁇ 85 mm as shown in FIG.
  • the maximum output voltage of a single cell of PIN type amorphous silicon solar cell 110 under 0.3 mWZ cm 2 is 0.38 V , the maximum output current density was 0. OS AmAZc m 2. Therefore, as shown in Fig. 13, the module is integrated by connecting twelve 1 cm x 2 cm single-cells 110 in series with the lead wire 12, and xenon with wavelengths of 400 nm or less and 1000 nm or more cut off.
  • the maximum output voltage when this module is set under excitation light of 1.3 mWZ cm 2 using a lamp as the light source can be calculated to be 4.56 V and the maximum output current to be 0.188 ⁇ .
  • the PIN-type amorphous silicon solar cell module has an electric double-layer capacitor 10 C with a capacity of 5 V and a IF of 0. Cannot be fully charged.
  • a single cell 110 of 1 cm x 2 cm was integrated in series with lead wires 12 to form a module, and wavelengths of 400 nm or less and 1000 nm or more were cut.
  • the charging time is more than four times longer than the photoelectric conversion module.
  • the dimension of the module is 49 mm ⁇ 98 mm as shown in FIG. 14, which is larger than the dimension (49 mm ⁇ 85 mm) of the module (photoelectric conversion element) 10A according to the present invention shown in FIG.
  • the silicon-based solar cell and the capacitor are combined even under a low illuminance such as an intensity of 1.3 mWZcm 2, which is 1/1000 of sunlight. It was found that compared to conventional power supplies, power could be stored more efficiently, and the size of the module could be made smaller than before, and consequently the portable power supply could be made smaller.
  • a single cell 10a was prepared in the same manner as in Example 3.
  • This single cell 10a was placed under simulated sunlight with an intensity of 10 OmW / c ni 2 and its current-voltage characteristics were measured.
  • the maximum output voltage V was 0.6V and the maximum output current density J 1 0.1111 Roh (: 111 2 Deatta [1 ⁇ 1.5: the spectral radiation distribution by the International electronic technology Commission (IEC) has decided].
  • 26 single cells 10a of 4 cm x 4 cm When the photoelectric conversion module 1 OA is created by connecting them in series and integrating 11 more in parallel, the maximum of this photoelectric conversion module 1 OA under simulated sunlight (AMI. 5) with an intensity of 10 OmWZcm 2 is obtained.
  • the output voltage is 15.6V and the maximum output current can be calculated as 177.76 mA.
  • a xenon lamp that Katsuhito wavelengths than less ⁇ Pi 1000 nm 400 nm as a light source, measurement of the current - voltage characteristic of the single cell 10 a 'under excitation light intensity 1.
  • SmWZc m 2 The maximum output voltage was 0.38 V and the maximum output current density was 0.09 ArnAZcm 2 .
  • the maximum output voltage of h 1 is 9.9 V, the maximum output current can be calculated as 66. 9 mA.
  • the PIN-type amorphous silicon solar cell (photoelectric conversion module) 10 A can produce 12 V, 200 F It is not possible to fully charge an electric double layer capacitor with a capacity of 12 V and 200 F.
  • This layer can be used as a counter electrode by forming a layer of the solid electrolyte itself up to the upper surface of the photosensitized electrode with good electrical connection in the solid electrolyte, sufficient hole transport ability, and An element having such a configuration is useful as a photoelectric conversion element such as a solar cell.
  • a photoelectric device comprising a transparent conductive electrode, an electron transporting layer composed of oxide fine particles having a pore structure, a hole transporting layer, a hole collecting electrode, and a photosensitizing compound adhered or fixed to the electron transporting layer. Since the conversion element is used in a portable power supply device, it has a high energy conversion efficiency even under low illuminance while storing the current output from the photoelectric conversion element in a storage capacitor, while fully exhibiting portability. The secondary battery can be charged efficiently, which is useful for energy saving.
  • a photoelectric device comprising a transparent conductive electrode, an electron transporting layer composed of oxide fine particles having a pore structure, a hole transporting layer, a hole collecting electrode, and a photosensitizing compound adhered or fixed to the electron transporting layer. Since the conversion element is used in the power supply unit, the energy conversion efficiency is high even under low illuminance, and the current output from the photoelectric conversion element can be stored in the storage capacitor to charge the battery efficiently, which is useful for energy saving. It is.

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Abstract

L'invention concerne un élément de conversion photoélectrique solide qui comporte une substance (8) solide servant à la fois de couche de transport de trous et d'électrode de collecte de trous. Cette substance solide contient en particulier un composé Π-conjugué.
PCT/JP2001/005856 2000-07-06 2001-07-05 Element de conversion photo-electrique solide, son procede de production, pile solaire pourvue d'un tel element de conversion photo-electrique solide, et dispositif d'alimentation en courant WO2002005354A1 (fr)

Priority Applications (1)

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AU2001269457A AU2001269457A1 (en) 2000-07-06 2001-07-05 Solid photo-electric converting element, process for producing the same, solar cell employing solid photo-electric converting element, and power supply

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2000-204726 2000-07-06
JP2000204726 2000-07-06
JP2000272006A JP2002083635A (ja) 2000-09-07 2000-09-07 携帯型電源装置，携帯型通信端末及び携帯型コンピュータ
JP2000-272006 2000-09-07
JP2000278322A JP2002093472A (ja) 2000-09-13 2000-09-13 乗物用電源装置
JP2000-278322 2000-09-13

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
US8153029B2 (en) 2006-12-28 2012-04-10 E.I. Du Pont De Nemours And Company Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof
US8318046B2 (en) 2002-09-24 2012-11-27 E I Du Pont De Nemours And Company Water dispersible polyanilines made with polymeric acid colloids for electronics applications
US8409476B2 (en) 2005-06-28 2013-04-02 E I Du Pont De Nemours And Company High work function transparent conductors
US8491819B2 (en) 2006-12-29 2013-07-23 E I Du Pont De Nemours And Company High work-function and high conductivity compositions of electrically conducting polymers
US8765022B2 (en) 2004-03-17 2014-07-01 E I Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
WO2020158876A1 (fr) * 2019-02-01 2020-08-06 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de cellule solaire, module d'alimentation électrique et dispositif électronique

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JPH05145096A (ja) * 1991-11-22 1993-06-11 Asahi Glass Co Ltd 透過型太陽電池
JPH07183555A (ja) * 1993-12-24 1995-07-21 Fuji Photo Film Co Ltd 塗布型太陽電池の製造方法
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EP0901175A2 (fr) * 1997-09-05 1999-03-10 Fuji Photo Film Co., Ltd. Dispositif de conversion photoélectrique et cellule solaire
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JPH11288745A (ja) * 1998-04-03 1999-10-19 Nikon Corp フレキシブル湿式太陽電池とその製造方法
JP2000285976A (ja) * 1999-03-31 2000-10-13 Fuji Photo Film Co Ltd 光電変換素子、太陽電池および太陽電池モジュール
JP2000336171A (ja) * 1999-05-26 2000-12-05 Mitsubishi Chemicals Corp ホール伝導性を有する超分岐高分子

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JPH0521824A (ja) * 1991-07-12 1993-01-29 Mitsubishi Paper Mills Ltd 光電変換素子
JPH05145096A (ja) * 1991-11-22 1993-06-11 Asahi Glass Co Ltd 透過型太陽電池
JPH07183555A (ja) * 1993-12-24 1995-07-21 Fuji Photo Film Co Ltd 塗布型太陽電池の製造方法
WO1996008022A1 (fr) * 1994-09-02 1996-03-14 Kieta Holding S.A. Cellule photovoltaique electrochimique
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EP0901175A2 (fr) * 1997-09-05 1999-03-10 Fuji Photo Film Co., Ltd. Dispositif de conversion photoélectrique et cellule solaire
JPH11288745A (ja) * 1998-04-03 1999-10-19 Nikon Corp フレキシブル湿式太陽電池とその製造方法
JP2000285976A (ja) * 1999-03-31 2000-10-13 Fuji Photo Film Co Ltd 光電変換素子、太陽電池および太陽電池モジュール
JP2000336171A (ja) * 1999-05-26 2000-12-05 Mitsubishi Chemicals Corp ホール伝導性を有する超分岐高分子

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8318046B2 (en) 2002-09-24 2012-11-27 E I Du Pont De Nemours And Company Water dispersible polyanilines made with polymeric acid colloids for electronics applications
US8765022B2 (en) 2004-03-17 2014-07-01 E I Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
US8409476B2 (en) 2005-06-28 2013-04-02 E I Du Pont De Nemours And Company High work function transparent conductors
US8153029B2 (en) 2006-12-28 2012-04-10 E.I. Du Pont De Nemours And Company Laser (230NM) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof
US8491819B2 (en) 2006-12-29 2013-07-23 E I Du Pont De Nemours And Company High work-function and high conductivity compositions of electrically conducting polymers
WO2020158876A1 (fr) * 2019-02-01 2020-08-06 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de cellule solaire, module d'alimentation électrique et dispositif électronique
CN113396491A (zh) * 2019-02-01 2021-09-14 株式会社理光 光电转换元件、太阳能电池模块、电源模块和电子装置

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