WO2018047550A1 - 太陽電池モジュール - Google Patents
太陽電池モジュール Download PDFInfo
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- WO2018047550A1 WO2018047550A1 PCT/JP2017/028475 JP2017028475W WO2018047550A1 WO 2018047550 A1 WO2018047550 A1 WO 2018047550A1 JP 2017028475 W JP2017028475 W JP 2017028475W WO 2018047550 A1 WO2018047550 A1 WO 2018047550A1
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- solar cell
- cell module
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- shaped molded
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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
- H01G9/2068—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
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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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
- H10F19/804—Materials of encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
- H10F19/90—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers
- H10F19/902—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells
- H10F19/904—Structures for connecting between photovoltaic cells, e.g. interconnections or insulating spacers for series or parallel connection of photovoltaic cells characterised by the shapes of the structures
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/20—Electrodes
- H10F77/206—Electrodes for devices having potential barriers
- H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/30—Coatings
- H10F77/306—Coatings for devices having potential barriers
- H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
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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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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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
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2081—Serial interconnection of cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 solar cell module.
- a solar cell using a resin film as a substrate has a merit that it is lightweight and flexible.
- Solar cells using these films as base materials include dye-sensitized solar cells, organic thin film solar cells, and perovskite solar cells. These solar cells usually include a cell having a structure in which a functional layer contributing to the movement of electrons and holes is sandwiched between two electrodes. More specifically, in the case of a dye-sensitized solar cell, an electrolyte layer is provided as a functional layer. In the case of an organic thin film solar cell or a perovskite solar cell, a donor layer and an acceptor layer are provided as functional layers.
- a solar cell is usually formed as a solar cell module having a take-out electrode connected to each of two electrodes including one or a plurality of cells, or by connecting a plurality of solar cell modules in series or in parallel. It is used in the form of a solar cell array.
- the entire solar cell module is made of resin in order to improve the long-term stability of the solar cell module by preventing leakage of electrolyte from the solar cell module and intrusion of moisture from the outside. It has been proposed to protect (see, for example, Patent Document 1).
- Patent Document 1 describes that the entire solar cell module of a dye-sensitized solar cell is vacuum-laminated using a resin film containing fluorine as a barrier packaging material for protecting the module from the external environment.
- an object of this invention is to provide the solar cell module which is excellent in the retention rate of photoelectric conversion efficiency which has a barrier packaging material which protects a solar cell module from the fluctuation
- the first electrode on the first substrate side and the second electrode on the second substrate side have functions.
- a solar cell module comprising: a first extraction electrode connected via a first electrical connection portion; and a second extraction electrode connected to the second electrode via a second electrical connection portion, wherein the solar cell
- the module has a gap between the outer periphery of the connection body and the barrier packaging material in the board surface direction including the surface direction of the first board and the surface direction of the second board, and at least within the gap.
- a solar cell module with a high retention rate of photoelectric conversion efficiency is obtained by the presence of the filling member in at least part of the gap in the substrate surface direction between the connection body and the barrier packaging material.
- the filling member contains a cured resin composition. If the resin composition in which the filling member is cured is included, the solar cell module can be hermetically sealed.
- the sealing portion is integral with the filling member. If at least a part of the sealing part is integrated with the filling member, the sealing airtightness of the solar cell module can be improved and the retention rate can be further improved.
- the filling member may include a frame-shaped molded body in which at least a part of the inner side surface shape extends along the side surface of the plurality of connected bodies.
- frame shape means a shape having at least an outer edge and an inner edge.
- the shape of these outer edges or inner edges is not particularly limited, and may be, for example, a rectangle, a polygon, a circle, an ellipse, and any other shape.
- the filling member includes the frame-shaped molded body, compared to the case where the frame-shaped molded body is not included, the periphery of the sealing portion is less likely to be curved, so that the generation of stress is suppressed and the barrier packaging material is less likely to peel off. The effect is expected. Further, by matching the thickness of the frame-shaped molded body with the thickness of the solar cell module, there is no step between the barrier packaging material sealing portion region and the other region in the solar cell module. In the subsequent process such as combination, the handleability is improved.
- the frame-shaped molded body is integral with a part of the barrier packaging material. If the frame-shaped molded body is integrated with a part of the barrier packaging material, the processability in the packaging process of the solar cell module can be improved. Moreover, if a frame-shaped molded object is integral with a part of barrier packaging material, the sealing property of a solar cell module can be improved further and the retention rate of a solar cell module can be improved further.
- the frame-shaped molded body has at least one conductor or a partial conductive layer, and the at least one conductor or conductive layer functions as the first or second extraction electrode.
- the conductor or the conductive layer it is preferable that at least a part of the conductor or the conductive layer is not covered with the barrier packaging material. If a frame-shaped molded body that can function as an extraction electrode is used, a solar cell module can be efficiently manufactured, and the extraction electrode can be disposed on any surface of the frame-shaped molded body, such as the bottom surface side of the solar cell module. It becomes possible.
- the conductive layer is a conductive layer formed on the frame-shaped molded body by a surface treatment using a conductive material. If the frame-shaped molded body has a conductive layer formed by surface treatment, the sealing property of the obtained solar cell module can be further improved and the retention rate can be further improved.
- the solar cell module of the present invention preferably includes an adhesive layer in at least a part of the gap between the first substrate and / or the second substrate and the barrier packaging material. If such an adhesive layer is interposed between the barrier packaging material and each substrate, the sealing property of the solar cell module can be further improved and the retention rate can be further improved. Furthermore, by selecting a material that takes into account the relationship with the refractive index of the substrate, it is possible to suppress reflection and improve light transmission to the inside.
- the functional layer may be an electrolyte layer
- the solar cell module may be a dye-sensitized solar cell module.
- a solar cell module with a high retention rate can be provided.
- FIG. 2 is a II-II sectional view showing a schematic structure of an example of the solar cell module shown in FIG.
- FIG. 4 is a IV-IV sectional view showing a schematic structure of an example of the solar cell module shown in FIG. 3.
- FIG. 3 It is a top view which shows schematic structure of an example of the frame-shaped molded object which can comprise the solar cell module of this invention.
- the solar cell module of the present invention is not particularly limited, and may be a solar cell module such as a dye-sensitized solar cell, an organic thin film solar cell, and a perovskite solar cell.
- the solar cell module of the present invention can be a solar cell module in which a plurality of photoelectric conversion cells (hereinafter also simply referred to as “cells”) are connected in series, for example, a solar cell module having a Z-type integrated structure.
- the solar cell module integrated structure includes, for example, a series connection structure such as a W-type module and a monolithic module, or a parallel connection structure, but is not limited thereto.
- the dye-sensitized solar cell module having a Z-type integrated structure as an example of the present invention is not particularly limited.
- FIG. 1 is a plan view and FIG. 2 is a cross-sectional view in the thickness direction.
- the solar cell module 100 which shows is shown.
- the solar cell module 100 shown in a plan view in FIG. 1 includes a barrier packaging material that includes a first substrate 3 that is a photoelectrode substrate and a second substrate 7 that is a counter electrode substrate that form a connection body of a plurality of cells. 13A and a barrier packaging material 13B (not shown in FIG. 1), and further includes a sealing portion 14 for sealing the barrier packaging material 13A and the barrier packaging material 13B.
- FIG. 2 shows a cross-sectional view taken along the line II-II in FIG.
- the solar cell module 100 is a dye-sensitized solar cell module including a connection body formed by connecting a plurality of (four in the illustrated example) cells partitioned by the partition walls 8 in series. It has a so-called Z-type integrated structure.
- the solar cell module 100 includes a first base 1 and a first photoelectrode 2 that is a plurality of (four in the illustrated example) first electrodes provided on the first base 1 so as to be spaced apart from each other.
- the photoelectrode 2 and the counter electrode 6 forming each cell are opposed to each other via the electrolyte layer 4 which is a functional layer. (Ie, so as to form a cell), and between the adjacent cells, the photoelectrode 2 of one cell and the counter electrode 6 of the other cell are electrically connected via the cell connection 9 It has a bonded structure.
- Each cell of the solar cell module 100 includes a photoelectrode 2, a counter electrode 6 facing the photoelectrode 2, and an electrolyte layer 4 provided between the photoelectrode 2 and the counter electrode 6.
- the solar cell module 100 includes a first extraction electrode 11A connected to the photoelectrode conductive layer 21 constituting the photoelectrode 2 via the first electrical connection portion 12A, and a counter electrode conductive constituting the counter electrode 6.
- a second extraction electrode 11B connected to the layer 61 via the second electrical connection portion 12B is provided.
- the barrier packaging materials 13A and 13B are sealed by a sealing portion 14 that is sealed with a cured sealing portion resin composition 15. As is clear from FIG. 1, the sealing portion 14 surrounds the outer periphery of the solar cell module 100 and separates the solar cell module 100 from the external environment.
- the internal space enclosed by the barrier wrapping materials 13A and 13B sealed by the sealing portion 14 includes the connection body of the plurality of cells described above.
- the solar cell module 100 includes the outer periphery of the connection body (in FIG. 2, defined by the side surface of the partition wall 8 and the end surface of the second base material 5), and the first extraction electrode 11A or the second extraction electrode 11B.
- the step that can be defined by If the gas occupies most of the space in contact with the step and the barrier wrapping material 13B, when the temperature of the solar cell module 100 rises, the sealing portion 14 is affected by the expansion of the gas.
- the barrier packaging material 13A and / or 13B may be peeled off. Therefore, in the present invention, the amount of gas that can be contained in the gap is reduced by disposing the filling member 30 in at least a part of the gap in the substrate surface direction between the outer periphery of the connection body and the barrier packaging material 13B. Thus, occurrence of peeling at the sealing portion 14 can be suppressed. Furthermore, since the distortion generated when the barrier packaging material is bonded around the step can be reduced by the filling member, the occurrence of peeling can be more effectively suppressed.
- the structure of the solar cell module of the present invention is not limited to the structure shown in FIGS.
- the first extraction electrode 11 ⁇ / b> A and the second extraction electrode 11 ⁇ / b> B extend from the same side of the sealing portion 14 formed on the outer periphery of the solar cell module 100.
- the solar cell module 100 may have a structure in which the first extraction electrode 11 ⁇ / b> A and the second extraction electrode 11 ⁇ / b> B are extended from different sides of the sealing portion 14.
- FIG. 1 in the solar cell module 100, the first extraction electrode 11 ⁇ / b> A and the second extraction electrode 11 ⁇ / b> B extend from the same side of the sealing portion 14 formed on the outer periphery of the solar cell module 100.
- the solar cell module 100 may have a structure in which the first extraction electrode 11 ⁇ / b> A and the second extraction electrode 11 ⁇ / b> B are extended from different sides of the sealing portion 14.
- both the first extraction electrode 11 ⁇ / b> A and the second extraction electrode 11 ⁇ / b> B are arranged near the center in the thickness direction of the solar cell module 100.
- the first extraction electrode 11A is not particularly limited as long as the first extraction electrode 11A is electrically connected to the photoelectrode 2 and insulated from the counter electrode 6.
- the first extraction electrode 11A is closer to the second base material 5 than the first base material 1. You may arrange
- the second extraction electrode 11 ⁇ / b> B may be disposed at a position closer to the first base material 1 than the second base material 5.
- substrate 3 of the solar cell module 100 shown in FIG.1 and FIG.2 is provided with the 1st base material 1 and the some photoelectrode 2 provided mutually spaced apart on the 1st base material 1.
- the photoelectrode 2 includes a photoelectrode conductive layer 21 provided on the first substrate 1 and a porous semiconductor fine particle layer 22 provided on a part of the photoelectrode conductive layer 21. .
- the photoelectrode conductive layer 21 is provided with a gap.
- the adjacent photoelectrodes 2 are provided so as to be electrically insulated from each other. This insulation is not particularly limited, and can be achieved, for example, by the partition walls 8 existing in the gaps between the photoelectrode conductive layers 21 adjacent to each other.
- the first substrate 1 is not particularly limited, and can be appropriately selected from known light-transmitting substrates.
- the 1st base material the known transparent base material which has transparency in visible fields, such as transparent resin and glass, is mentioned.
- resin shape-formed, ie, a resin film As the 1st base material 1, it is preferable to use resin shape-formed, ie, a resin film.
- the resin film substrate is inferior in the barrier property of the substrate itself as compared with a substrate such as glass, but the barrier property can be greatly improved by taking the structure of the present invention.
- a resin film as the first base material 1 it is possible to apply lightness and flexibility to the solar cell module, and thus it can be applied to various applications.
- transparent resins examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), and polyarylate (PAr).
- Synthetic resins such as polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), transparent polyimide (PI), and cycloolefin polymer (COP).
- the photoelectrode conductive layer 21 is not particularly limited, and includes a conductive layer made of a metal mesh composed of Au, Ag, Cu, metal nanoparticles such as Ag nanoparticles, minute Ag wires, and the like. Includes conductive layers formed by coating, conductive layers made of complex metal oxides such as indium-tin oxide (ITO), indium-zinc oxide (IZO), and fluorine-doped tin (FTO), carbon nanotubes, graphene, etc. And a conductive layer made of a conductive polymer such as PEDOT / PSS (poly (3,4-ethylenedioxythiophene) polystyrene sulfonate). These materials can be appropriately selected depending on compatibility with other materials.
- PEDOT / PSS poly (3,4-ethylenedioxythiophene) polystyrene sulfonate
- a plurality of these conductive layers may be laminated on the base material, or various conductive materials as described above that can be used for forming these conductive layers are mixed to form one conductive layer. It may be formed.
- a known forming method such as a method in which sputtering and etching are combined or screen printing can be used.
- an undercoat layer (not shown) can be provided on the photoelectrode conductive layer 21.
- the electrolytic solution reaches the photoelectrode conductive layer 21 through the porous semiconductor fine particle layer 22, and passes from the photoelectrode conductive layer 21 to the electrolyte layer 4.
- An internal short circuit phenomenon called reverse electron transfer in which electrons leak can occur. For this reason, a reverse current unrelated to the light irradiation may occur and the photoelectric conversion efficiency may be reduced. Therefore, an undercoat layer can be provided on the photoelectrode conductive layer 21 to prevent such an internal short-circuit phenomenon.
- the adhesion between the porous semiconductor fine particle layer 22 and the photoelectrode conductive layer 21 can be improved by providing an undercoat layer on the photoelectrode conductive layer 21.
- the undercoat layer is not particularly limited as long as it is a substance that can prevent the internal short circuit phenomenon (interfacial reaction is unlikely to occur).
- it may be a layer containing a material such as titanium oxide, niobium oxide, or tungsten oxide.
- a method for forming the undercoat layer a method in which the above material is directly sputtered on the transparent conductive layer, a solution in which the above material is dissolved in a solvent, a solution in which a metal hydroxide that is a precursor of a metal oxide is dissolved, Alternatively, there is a method in which a solution containing a metal hydroxide obtained by dissolving an organometallic compound in a mixed solvent containing water is applied on the conductive layer 21 for photoelectrodes, dried, and sintered as necessary. is there.
- the porous semiconductor fine particle layer 22 carrying (adsorbing) a sensitizing dye is not particularly limited, and is a porous semiconductor fine particle layer containing particles of an oxide semiconductor such as titanium oxide, zinc oxide, tin oxide.
- a porous semiconductor fine particle layer formed by adsorbing a sensitizing dye such as an organic dye or a metal complex dye can be used.
- organic dyes include cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, and perylene dyes.
- the metal complex dye examples include bipyridine complexes, phthalocyanine complexes, porphyrin complexes of metals such as iron, copper, and ruthenium.
- Examples of typical sensitizing dyes include N3, N719, N749, D102, D131, D150, N205, HRS-1, and HRS-2.
- the organic solvent for dissolving the sensitizing dye is preferably degassed and purified by distillation in advance in order to remove moisture and gas present in the solvent.
- Organic solvents include alcohols such as methanol, ethanol, propanol, nitriles such as acetonitrile, halogenated hydrocarbons, ethers, amides, esters, carbonates, ketones, hydrocarbons, aromatics, nitromethane, etc. Is preferred. Two or more of these solvents can be mixed and used.
- a known forming method such as screen printing or coating can be used.
- a method for adsorbing the sensitizing dye to the porous semiconductor fine particle layer a known method such as immersion of the porous semiconductor fine particle layer in a solution containing the sensitizing dye can be used.
- the second substrate 7 of the solar cell module 100 includes a second base material 5 and a plurality of counter electrodes 6 provided on the second base material 5 so as to be separated from each other.
- the counter electrode 6 includes a counter electrode conductive layer 61 provided on the second substrate 5 and a catalyst layer 62 provided on a part of the counter electrode conductive layer 61.
- the counter electrode conductive layer 61 is provided with a gap.
- the catalyst layer 62 faces the porous semiconductor fine particle layer 22 of the photoelectrode 2.
- the counter electrodes 6 adjacent to each other are provided so as to be electrically insulated from each other. This insulation is not particularly limited, and can be achieved, for example, by interposing the partition wall 8 in the gap between the opposing electrodes 6 adjacent to each other.
- the 2nd base material 5 it is the same base material as the 1st base material 1, or the base material which does not have transparency like foil, plates, such as titanium, SUS, and aluminum, and other sun A base material free from corrosion by battery members can be used. Especially, it is preferable to form the 2nd base material 5 using a resin film for the same reason as the 1st base material 1.
- a conductive layer similar to the photoelectrode conductive layer 21 can be used as the counter electrode conductive layer 61.
- the catalyst layer 62 is not particularly limited, and any catalyst containing a component that can function as a catalyst such as a conductive polymer, a carbon nanostructure, a noble metal, and a mixture of the carbon nanostructure and the noble metal. Layers can be used.
- the conductive polymer include poly (thiophene-2,5-diyl), poly (3-butylthiophene-2,5-diyl), and poly (3-hexylthiophene-2,5-diyl).
- Polythiophene such as poly (2,3-dihydrothieno- [3,4-b] -1,4-dioxin) (PEDOT); polyacetylene and derivatives thereof; polyaniline and derivatives thereof; polypyrrole and derivatives thereof; poly (p-xylene) Tetrahydrothiophenium chloride), poly [(2-methoxy-5- (2'-ethylhexyloxy))-1,4-phenylenevinylene], poly [(2-methoxy-5- (3 ', 7'- Dimethyloctyloxy) -1,4-phenylenevinylene)], poly [2-2 ′, 5′-bis (2 ′′ -ethylhexyloxy) phenyl] -1,4 Polyphenylene vinylenes such as -phenylene vinylene]; and the like.
- PEDOT poly (2,3-dihydrothieno- [3,4-b] -1,4-dioxin)
- PEDOT poly
- Examples of the carbon nanostructure include natural graphite, activated carbon, artificial graphite, graphene, carbon nanotube, and carbon nanobud.
- the noble metal is not particularly limited as long as it has a catalytic action, and a known noble metal such as metal platinum, metal palladium, and metal ruthenium can be appropriately selected and used.
- the method for forming the catalyst layer is not particularly limited, and a known method can be appropriately selected and used.
- a conductive liquid, a carbon nanostructure, a noble metal, or a mixture obtained by dissolving or dispersing both a carbon nanostructure and a noble metal in an appropriate solvent is applied or sprayed onto the conductive film, and the mixture is mixed. It can be performed by drying the solvent of the liquid.
- a binder may be further added to the mixed solution.
- the binder from the viewpoint of dispersibility of the carbon nanostructure and adhesion to the substrate, a hydroxyl group, a carboxyl group, a sulfonyl group It is preferable to use a polymer having a functional group such as a phosphate group and a sodium salt of these functional groups. Moreover, it can also form into a film by the existing formation methods, such as screen printing, vapor deposition, and sputtering.
- the catalyst layer is a carbon nanotube satisfying an average diameter (Av) of carbon nanotubes and a standard deviation ( ⁇ ) of diameter satisfying 0.60> 3 ⁇ / Av> 0.20 (hereinafter sometimes referred to as formula (A)).
- Av average diameter
- ⁇ standard deviation
- specific carbon nanotubes is a general term for a set of predetermined carbon nanotubes constituting the carbon nanotube, and “diameter” means an outer diameter of the predetermined carbon nanotube.
- the average diameter (Av) and standard deviation ( ⁇ ) of the diameter of a specific carbon nanotube are a sample average value and a sample standard deviation, respectively. They are determined as an average value and a standard deviation when measuring the diameter of 100 randomly selected carbon nanotubes under observation with a transmission electron microscope. 3 ⁇ in the formula (A) is obtained by multiplying the obtained standard deviation ( ⁇ ) by 3.
- a counter electrode having excellent catalytic activity can be obtained by using specific carbon nanotubes. From the viewpoint of improving the characteristics of the obtained counter electrode, 0.60> 3 ⁇ / Av> 0.25 is preferable, and 0.60> 3 ⁇ / Av> 0.50 is more preferable.
- 3 ⁇ / Av represents the diameter distribution of a specific carbon nanotube, and the larger this value, the wider the diameter distribution.
- the diameter distribution is preferably a normal distribution.
- the diameter distribution is measured by measuring the diameters of 100 randomly selected carbon nanotubes that can be observed using a transmission electron microscope, and using the results, the horizontal axis represents the diameter and the vertical axis represents the frequency. And plotting the resulting data and approximating with Gaussian.
- the value of 3 ⁇ / Av can also be increased by combining a plurality of types of carbon nanotubes obtained by different production methods, but in this case, it is difficult to obtain a normal distribution of diameters.
- the specific carbon nanotube may be a single carbon nanotube, or may be a single carbon nanotube mixed with another carbon nanotube in an amount that does not affect the diameter distribution.
- the specific carbon nanotube is a known method, for example, a substrate having a catalyst layer for producing carbon nanotubes (hereinafter sometimes referred to as “catalyst layer for producing CNT”) on the surface (hereinafter referred to as “substrate for producing CNT”).
- a catalyst layer for producing CNT hereinafter sometimes referred to as “catalyst layer for producing CNT”
- substrate for producing CNT a substrate having a catalyst layer for producing CNT
- CVD method chemical vapor deposition method
- a small amount of oxidant is present in the system, so that CNT It can be obtained by a method (supergrowth method) of dramatically improving the catalytic activity of the production catalyst layer (for example, International Publication No. 2006/011655).
- the carbon nanotube produced by the super growth method may be referred to as SGCNT.
- the counter electrode including a catalyst layer composed of specific carbon nanotubes for example, a dispersion containing specific carbon nanotubes is prepared, this dispersion is applied onto a substrate, and the resulting coating film is dried.
- the catalyst layer can be formed by forming the catalyst layer.
- the partition wall 8 of the solar cell module 100 is provided between the first substrate 3 and the second substrate 7 and surrounds each of the electrolyte layer 4 and the cell connection portion 9.
- the space in which the electrolyte layer 4 is provided and the space in which the cell connection portion 9 is provided are partitioned by the first substrate 3, the second substrate 7, and the partition walls 8.
- the partition wall 8 includes the photoelectrode conductive layer 21 of the photoelectrode 2 of the first substrate 3 and the second substrate 7 on one side in the width direction of each cell (left side in FIG. 2).
- the counter electrode conductive layer 61 of the counter electrode 6 (the portion located on the other side in the width direction than the portion where the catalyst layer 62 is formed) is provided.
- the electrolyte layers 4 and the cell connection portions 9 are alternately provided between the partition walls 8.
- the partition wall 8 is not particularly limited as long as it can adhere the first substrate 3 and the second substrate 7 and seal the electrolyte layer 4.
- the partition wall 8 is preferably excellent in adhesion between substrates, resistance to an electrolyte (chemical resistance), and high temperature and high humidity durability (moisture heat resistance).
- the partition wall material that can form such a partition wall 8 include a non-conductive thermoplastic resin, a thermosetting resin, and an active radiation (light, electron beam) curable resin.
- (meth) acryl means “acryl” or “methacryl”.
- a photocurable acrylic resin is preferable from the viewpoint of handleability.
- the partition wall 8 can be configured using a film formed by forming various resins as described above into a sheet shape.
- the electrolyte layer 4 that is a functional layer of the solar cell module 100 is provided in a space surrounded by the porous semiconductor fine particle layer 22 of the photoelectrode 2, the catalyst layer 62 of the counter electrode 6, and the partition walls 8.
- the electrolyte layer 4 is not particularly limited, and can be formed using any electrolytic solution, gel electrolyte, or solid electrolyte that can be used in the dye-sensitized solar cell.
- the cell connection part 9 of the solar cell module 100 electrically connects cells adjacent to each other in series.
- the cell connection portion 9 includes the photoelectrode conductive layer 21 of the photoelectrode 2 of the cell located on the right side in FIG. 2 and the counterelectrode conductive layer of the counter electrode 6 of the cell located on the left side in FIG. 61 is electrically connected.
- the cell connection portion 9 of the solar cell module 100 includes the wiring 91 formed on the photoelectrode conductive layer 21 of the photoelectrode 2 so as to be separated from the porous semiconductor fine particle layer 22, the first substrate 3, and the second substrate. 7 and the conductive resin composition 92 filled in the space surrounded by the partition walls 8.
- the cell connection part 9 is formed using the wiring 91 and the conductive resin composition 92.
- the cell connection part is a conductive resin. You may form using only a composition.
- the wiring may be formed on the counter electrode conductive layer 61 of the counter electrode 6.
- the wiring 91 is not particularly limited, and wiring made of a conductive material such as metal and metal oxide can be used. Among these, from the viewpoint of increasing the photoelectric conversion efficiency of the dye-sensitized solar cell module by reducing the resistance of the cell connection portion 9, the wiring 91 is a metal wiring such as a copper wiring, a gold wiring, a silver wiring, or an aluminum wiring. It is preferable to use it.
- a method for forming the wiring 91 on the photoelectrode conductive layer 21 a known forming method such as sputtering or screen printing can be used.
- the conductive resin composition 92 is not particularly limited, and it is preferable to use a composition containing a resin and conductive particles.
- the resin of the conductive resin composition 92 is not particularly limited, and is a (meth) acrylic resin; epoxy resins such as bisphenol type epoxy resin, novolac type epoxy resin, cyclic epoxy resin, and alicyclic epoxy resin; silicone Resin; and the like.
- Arbitrary hardening agents such as a radical initiator, a cationic hardening agent, and an anionic hardening agent, can be used for the said resin, and a polymerization form is not specifically limited, such as addition polymerization and ring-opening polymerization.
- the resin as the partition wall material and the resin of the conductive resin composition 92 may be the same or different.
- the conductive particles of the conductive resin composition 92 are not particularly limited.
- metal particles such as Ag, Au, Cu, Al, In, Sn, Bi, Pb, and their oxides, conductive Carbon particles, and particles obtained by coating the surface of organic compound particles such as resin particles and inorganic compound particles with a conductive material such as a metal such as Ag, Au, or Cu or an oxide of these metals, such as Au / Ni Particles coated with an alloy can be used.
- the average particle diameter of electroconductive particle is 0.5 micrometer or more and 30 micrometers or less.
- the content rate of electroconductive particle is 0.1 volume% or more and 90 volume% or less.
- the cell connection part 9 using the conductive resin composition 92 described above is not particularly limited.
- the cell connection part 9 includes an uncured resin and conductive particles at a position where the cell connection part 9 is formed. It can be formed by filling a cured conductive resin composition and curing the filled uncured conductive resin composition.
- the first extraction electrode 11A and the second extraction electrode 11B connected to the photoelectrode 2 and the counter electrode 6 are not particularly limited, and a conductor formed of a general conductive material is used. Have. Examples of such a conductor include a metal material selected from the group consisting of copper, aluminum, nickel, titanium, iron, and the like, and a conductor formed of an alloy material including these metal materials. Among them, an electrode using copper as a conductor or a material using stainless steel as a base material is preferable.
- the 2nd electrical connection part 12B which connects 11B is not specifically limited, It can form with common electrical connection materials, such as a conductive resin composition and solder.
- a conductive resin composition the known composition containing conductive materials, such as a metal, a metal oxide, and a conductive carbon material, and arbitrary resin similarly to the conductive resin composition 92 mentioned above. Can be used.
- a solder the thing containing tin, silver, copper, bismuth, lead, a flux component, etc. can be used.
- the first electrical connection portion 12 ⁇ / b> A and the second electrical connection portion 12 ⁇ / b> B are respectively connected to the photoelectrode 2 or the counter electrode 6 via a collector line formed in the same manner as the wiring 91. It may be connected.
- the sealing portion 14 is sealed with a cured sealing portion resin composition 15.
- a resin composition for sealing parts it does not specifically limit, A photocurable resin composition, a thermosetting resin composition, and a thermoplastic resin composition can be mentioned. Especially, it is preferable to use a photocurable resin composition as a resin composition for sealing parts. If the resin composition for sealing portions is photo-curable, deterioration due to heating in the manufacturing process of the organic solar cell can be prevented, and the electrical characteristics of the solar cell module can be improved. Furthermore, since the photocurable resin can be cured in a short time, it can be expected to obtain a solar cell module with good production efficiency.
- the photocurable resin composition examples include an ultraviolet curable resin composition and a visible light curable resin composition, and it is preferable to use an ultraviolet curable resin composition.
- the ultraviolet curable resin composition include a (meth) acrylic resin composition, an epoxy resin composition, a fluorine resin composition, and an olefin resin composition. It is preferable to use a composition, an epoxy resin composition, or a fluorine resin composition. These may be used alone or in combination of two or more.
- the thermosetting resin composition include a thermosetting resin composition that can be cured at a temperature at which the electrolyte constituting the electrolyte layer 4 is not vaporized. More specifically, thermosetting resin compositions having a curing temperature in the range of 60 ° C.
- thermosetting resin composition examples include, for example, a (meth) acrylic resin composition, an epoxy resin composition, a fluorine resin composition, a silicone resin composition, an olefin resin composition, and a polyisobutylene resin. Examples thereof include compositions. These may be used alone or in combination of two or more.
- thermoplastic resin composition examples include a thermoplastic resin having a melting point at a temperature that does not vaporize the liquid in the electrolyte layer. More specifically, a thermoplastic resin having a melting point in the range of 80 ° C.
- the sealing part 14 can be comprised by the several member which consists of the same or different raw material.
- the sealing part 14 may be comprised from the sealing member which consists of a metal or resin, and the cured resin composition for sealing parts which adhere
- the barrier packaging materials 13A and 13B impart durability to the solar cell module 100 under high temperature and high humidity environmental conditions to which the solar cell module 100 can be exposed. Therefore, the barrier packaging materials 13A and 13B are preferably packaging bodies having a barrier property against gas and water vapor. Further, in FIG. 2, two barrier packaging materials 13A and 13B are illustrated as barrier packaging materials. As is clear from FIG. 2, the barrier packaging material 13A is disposed on the first substrate 3 side, and the barrier packaging material 13B is disposed on the second substrate 7 side.
- the barrier packaging material is not limited to the two sheet-like packaging bodies respectively disposed in the upper and lower thickness directions of the solar cell module as shown in FIG. Furthermore, it may be a cylindrical film opened in the depth direction (left and right direction in FIG. 2) of a plurality of cells constituting the solar cell module.
- the inclusion mode of the first substrate 3 and the second substrate 7 by the barrier wrapping materials 13A and 13B is not particularly limited, and the first substrate 3 / second substrate 7 and the barrier wrapping material 13A / 13B have an adhesive. May be in close contact with each other, and includes the first substrate 3 / second substrate 7, but there is a space between these and the barrier wrapping material 13A / 13B. It may be in a state of being filled with a filler that is difficult to pass gas. More specifically, the barrier packaging material 13A disposed on the first substrate 3 side and the first substrate 3 are in close contact via an adhesive layer (not shown), and the barrier disposed on the second substrate 7 side. The packaging material 13B and the second substrate 7 may be in close contact via an adhesive layer (not shown).
- the sealing property of the solar cell module can be further improved.
- the adhesive layer is disposed on the first substrate 3 side that is the light incident side substrate, if there is an adhesive layer between the barrier packaging material 13A and the first substrate 3, the barrier packaging material 13A and the first substrate 3 No air layer is interposed between the first substrate 1 and the first substrate 3.
- the air layer has a refractive index greatly different from that of the barrier packaging material 13 ⁇ / b> A and the first base material 1. For this reason, the refractive index difference at the interface of the laminated structure of the barrier packaging material 13A-air layer-first substrate 1 becomes large.
- the space between the barrier packaging material 13A and the first base material 1 is filled with an adhesive layer, so that the refractive index difference can be reduced and loss due to interface reflection can be reduced. Furthermore, it can suppress that an interference fringe generate
- Such a material can be selected from the materials listed as the partition material while taking into consideration the material of the barrier packaging material 13A and the material of the first base material 1, for example.
- the solar cell module is a dye-sensitized solar cell module
- examples of the filler that is difficult to pass water vapor or gas include liquid or gel paraffin, silicone, phosphate ester, aliphatic ester and the like.
- the barrier packaging materials 13A and 13B preferably have a water vapor permeability of 0.1 g / m 2 / day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90% (90% RH), and 0.01 g / m 2 / day or less is more preferable, 0.0005 g / m 2 / day or less is further preferable, and 0.0001 g / m 2 / day or less is particularly preferable.
- the barrier packaging materials 13A and 13B preferably have a total light transmittance of 50% or more, more preferably 70% or more, and still more preferably 85% or more. Such total light transmittance can be measured, for example, according to JIS K7361-1.
- the barrier packaging materials 13A and 13B may be a film or a thin plate in which a barrier layer having low water vapor and gas permeability is installed on a plastic support.
- barrier films with low gas permeability include those deposited with silicon oxide or aluminum oxide (Japanese Patent Publication No. 53-12953, Japanese Patent Laid-Open No. 58-217344), and those having an organic-inorganic hybrid coating layer (Japanese Patent Laid-Open No. 2000-2000). 323273, Japanese Unexamined Patent Application Publication No. 2004-25732), those having an inorganic layered compound (Japanese Unexamined Patent Application Publication No. 2001-205743), laminated inorganic materials (Japanese Unexamined Patent Application Publication No.
- the barrier packaging material may be in a film shape or a thin plate shape in the integrally molded body. I do not care.
- the filling member 30 is present.
- the filling member 30 is preferably in contact with the outer periphery of the connection body within the gap.
- the filling member 30 preferably occupies 90% or more of the total volume of the gap, more preferably 95% or more, and even more preferably 99% or more. This is because by suppressing the volume that the gas can occupy in the gap, it is possible to suppress the gas from expanding and causing the sealing portion 14 to peel when the temperature of the solar cell module rises.
- the filling member 30 can include a cured resin composition and / or a frame-shaped molded body in which at least a part of the inner side surface shape extends along the side surface of the connection body of the plurality of cells.
- the frame-shaped molded body may have a shape like a frame-shaped molded body 31 shown in FIG. Since the filling member includes the frame-shaped molded body 31, compared with the case where the frame-shaped molded body 31 is not included, the periphery of the sealing portion is less likely to be curved, so that generation of stress is suppressed, and the barrier packaging material 13 ⁇ / b> A and The effect that 13B becomes difficult to peel is expected.
- the thickness of the frame-shaped molded body 31 with the thickness of the solar cell module 100, there is no step between the barrier packaging material sealing portion region and the other region in the solar cell module. Even in a later process such as combining with a member, handleability is improved.
- the filling member 30 is preferably integral with at least a part of the sealing portion 14. If the filling member 30 is integrated with at least a part of the sealing part 14, the sealing property of the solar cell module is improved, the retention rate is further improved, and the processability can be improved by integrally molding. It is because it improves.
- the filling member is integral with at least a part of the sealing part means that the filling member and at least a part of the sealing part are seamlessly formed of the same material. means.
- the filling member 30 is formed of the sealing portion resin composition 15 to form a structure in which the “filling member is integral with at least a part of the sealing portion”. Can do.
- the frame-shaped molded body 31 constituting the filling member also functions as a part of the sealing portion that seals the gap between the barrier packaging materials 13A and 13B.
- a metal sealing member is interposed between the barrier packaging materials 13A and 13B as a structure in which “the filling member is integral with at least a part of the sealing portion”, and the metal sealing is performed.
- a structure in which the member and the upper and lower barrier wrapping materials 13A and 13B are bonded by a cured product of the resin composition for sealing portion having the same composition as that of the filling member 30 is exemplified.
- the frame-shaped molded object 31 can select various materials, such as resin and a metal, and these composite materials, without being specifically limited.
- the metal material aluminum, SUS, copper, titanium, nickel, or the like can be used.
- the cured resin composition forming the filling member 30 and the resin composition used for forming the frame-shaped molded body 31 are not particularly limited and are those described above as the “resin composition for the sealing portion”. The same resin composition as can be used. Even if the frame-shaped molded body 31 is made of the same material as the resin composition forming the filling member 30 or the sealing portion resin composition, the frame-shaped molded body 31 of the solar cell module 100 is not limited.
- Presence / absence can be determined by observing the cut surface of the solar cell module 100 and visually or microscopically determining whether or not there is an adhesive interface between the resins, or by analyzing the surface of the cut surface. Furthermore, it is preferable that moisture permeability of the frame-shaped molded body is suppressed as compared with the barrier packaging material sealing portion.
- a method for suppressing moisture permeability there are a method of reducing the moisture permeability of the frame-shaped molded body itself, or a method of forming a metal material layer having a low moisture permeability on at least a part of the surface of the frame-shaped molded body. is there.
- the distance between the barrier packaging materials 13A and 13B is apparently increased, but moisture permeation into the solar cell module 100 can be suppressed.
- a conductive material such as a metal
- an insulating portion is appropriately formed by coating or the like at a place where insulation is required for mounting on the solar cell module.
- FIG. 3 is a plan view of the solar cell module 101 in which the filling member 30 is formed of the frame-shaped molded body 31 as viewed from the second substrate 7 side.
- the frame-shaped molded body 31 has a rectangular frame shape.
- the frame-shaped molded body 31 has two conductors, and these conductors function as the first extraction electrode 11A and the second extraction electrode 11B, respectively.
- at least a part of the first extraction electrode 11A and the second extraction electrode 11B is covered with the barrier packaging material 13B on the upper surface of the solar cell module 101 adjacent to the second substrate 7. Not.
- the inner side surface shape of the frame-shaped molded body 31 is a shape along the side surface of the connection body of a plurality of cells. More specifically, the inner surface shape of the frame-shaped molded body 31 includes the first substrate 3, the first electrical connection portion 12A, the second substrate 7, the second electrical connection portion 12B, and a connection body of a plurality of cells. It is the shape which follows the side surface of the two partition walls 8 which form the both ends.
- the gap between the second extraction electrode 11B may be filled with a cured resin composition.
- the gap between the first extraction electrode 11A or the second extraction electrode 11B and the connection body of a plurality of cells adjacent to each other is similarly filled with the cured resin composition. Also good.
- resin compositions it does not specifically limit, The resin composition similar to what was mentioned above as "resin composition for sealing parts" can be used.
- the frame-shaped molded body 31 may be an integral molded body that is partially integrated with the barrier packaging material 13A or 13B.
- the frame-shaped molded body is integral with a part of the barrier packaging material means that the barrier packaging material and the frame-shaped molded body are formed of the same material. Means seamless. In this case, the processability in the packaging process of the solar cell module 100 can be improved. Further, since there is no seam between the barrier packaging material 13A or 13B and the frame-shaped molded body 31, the hermeticity of the solar cell module 101 can be further improved, and the retention rate of the solar cell module 100 can be further increased. .
- the first extraction electrode 11A and the second extraction electrode 11B are conductive layers formed on the frame-shaped molded body 31 by surface treatment using a conductor provided in the frame-shaped molded body 31 or a conductive material.
- a surface treatment method a surface treatment method by a dry process such as vapor deposition or a surface treatment method by a wet process such as plating can be appropriately used.
- the conductive material used for the surface treatment a general metal material or alloy material as described above can be used as the conductor forming material of the extraction electrode. If the frame-shaped molded body 31 has a conductive layer formed by surface treatment, the sealing property of the obtained solar cell module can be further improved and the retention rate can be further improved.
- the conductor may have a form formed not only on the surface of the frame-shaped molded body 31 but also inside the frame-shaped molded body 31.
- a conductor penetrating the inside of the frame-shaped molded body 31 can be formed by preparing a penetrating portion in the frame-shaped molded body 31 in advance and filling it with solder, conductive resin, or the like.
- the frame-shaped molded body 31 is made of a conductive material, the surface may be covered with an insulating resin or the like, and the partially exposed conductive surfaces may be used as the first extraction electrode 11A and the second extraction electrode 11B.
- the solar cell module 100 having the above-described configuration is not particularly limited, and can be manufactured by the following procedure, for example. Specifically, first, the first substrate 3 including the photoelectrode 2 is manufactured, and then the wiring 91 is formed on the manufactured first substrate 3. Next, an uncured conductive resin composition 92 is applied at a position overlapping the wiring 91, and a partition wall material is applied so as to surround the photoelectrode conductive layer 21 with the applied conductive resin composition 92 interposed therebetween. To do. Then, a component constituting the electrolyte layer 4 such as an electrolytic solution is filled in the region where the partition wall material is applied. Thereafter, the second substrate 7 including the counter electrode 6 is overlapped with the first substrate 3. Further, the uncured conductive resin composition 92 is cured to form the cell connection portion 9 and the first substrate 3 and the second substrate 7 are firmly bonded to connect a plurality of cells including a pair of electrode substrates. Get the body.
- the first extraction electrode 11A and the second extraction electrode 11B are bonded to the photoelectrode 2 and the counter electrode 6 provided in the obtained connection body of the plurality of cells via a conductive adhesive, respectively (extraction) Electrode mounting step). And a resin composition is apply
- the barrier packaging material 13A is stacked.
- a pair of upper and lower pressing members each having a protruding surface made of a rubber material is used to sandwich a structure that sandwiches a connection body with the extraction electrodes 11A and 11B attached between the barrier packaging materials 13A and 13B from the upper and lower surfaces. Indent (pinch process).
- the barrier packaging materials 13A and 13B and the connection body are brought into close contact with each other through the resin composition to obtain the solar cell module 100 having the structure described with reference to FIG. 1 and FIG. it can.
- the frame-shaped molded object 31 is prepared first.
- the frame-shaped molded body 31 may have a conductive layer formed by surface treatment using a conductive material.
- the frame-shaped molded body 31 can be formed by pouring the resin composition as described above into a mold having a desired shape and curing it. And with respect to the obtained frame-shaped molded object 31, taking-out electrodes 11A and 11B are attached through a resin composition. Then, the solar cell having the structure described with reference to FIGS. 3 and 4 with the frame-shaped molded body 31, the extraction electrodes 11A / 11B, and the barrier packaging materials 13A and 13B in close contact with each other through the resin composition. The battery module 101 can be obtained.
- the light amount of the light source was adjusted to 1 sun (about 100,000 lux AM1.5G, 100 mWcm-2 (JIS C 8912 class A)), and the solar cell module was irradiated.
- the output voltage was measured while changing the bias voltage from 0 V to 0.8 V in units of 0.01 V under 1 sun light irradiation, and current-voltage characteristics were obtained.
- measurement was performed by stepping the bias voltage from 0.8 V to 0 V in the reverse direction, and the average value of the measurements in the forward direction and the reverse direction was used as photocurrent data.
- the initial photoelectric conversion efficiency (%) was calculated from the current-voltage characteristics and photocurrent data thus obtained.
- Example 1 ⁇ Preparation of dye solution> 72 mg of ruthenium complex dye (N719, Solaronics) was placed in a 200 mL volumetric flask. 190 mL of dehydrated ethanol was mixed and stirred. After stoppering the volumetric flask, the mixture was stirred for 60 minutes by vibration with an ultrasonic cleaner. After keeping the solution at room temperature, dehydrated ethanol was added to make a total volume of 200 mL to prepare a dye solution.
- ruthenium complex dye N719, Solaronics
- a transparent conductive substrate obtained by coating a transparent conductive layer (indium tin oxide (ITO)) as a conductive layer for photoelectrodes on a transparent substrate (polyethylene naphthalate film, thickness 200 ⁇ m) as a base material for photoelectrodes
- a transparent conductive layer indium tin oxide (ITO)
- ITO indium tin oxide
- a transparent substrate polyethylene naphthalate film, thickness 200 ⁇ m
- conductive silver paste K3105, manufactured by Pernox Co., Ltd.
- the obtained transparent conductive substrate having wiring was set on a coating coater with the wiring formation surface facing up, and an organic PC-600 solution (manufactured by Matsumoto Fine Chemical) diluted to 1.6% was swept with a wire bar ( 10 mm / sec).
- the obtained coating film was dried at room temperature for 10 minutes, and then further heated and dried at 150 ° C. for 10 minutes to produce an undercoat layer on the transparent conductive substrate.
- Laser treatment was performed on the undercoat layer forming surface of the transparent conductive substrate at intervals corresponding to the photoelectrode cell width to form insulating wires.
- a porous semiconductor fine particle layer is applied to a mask film (bottom: PC-542PA manufactured by Fujimori Kogyo Co., Ltd., NBO-0424 manufactured by Fujimori Kogyo Co., Ltd.) obtained by stacking two layers of protective films coated with an adhesive layer on a polyester film. An opening (length: 60 mm, width 5 mm) for forming was punched. The processed mask film was bonded to the current collector forming surface of the transparent conductive substrate on which the undercoat layer was formed so that air bubbles would not enter.
- the first layer of the mask film is for the purpose of preventing the dye from adhering to unnecessary portions
- the second layer is for the purpose of preventing the porous semiconductor fine particles from adhering to the unnecessary portions.
- a conductive surface having a resistance of 13 ohm / sq.) was subjected to laser treatment at intervals corresponding to the platinum film pattern width to form an insulating wire.
- a metal mask with punched openings (length: 60 mm, width: 5 mm) is overlaid, and six platinum film patterns (catalyst layers) are formed by a sputtering method.
- a counter electrode substrate having transmittance was obtained. At this time, when the photoelectrode substrate and the counter electrode substrate were superposed with their conductive surfaces facing each other, the porous semiconductor fine particle layer and the catalyst layer were made to coincide with each other.
- UV curable sealant TB3035B manufactured by ThreeBond Co., Ltd., absorption wavelength: 200 nm to 420 nm
- a dispenser device After that, a predetermined amount of electrolyte solution is applied to the catalyst layer portion, and is laminated in a reduced pressure environment so that the rectangular catalyst layer and the porous semiconductor fine particle layer of the same type face each other using an automatic laminating device.
- Light irradiation was performed from the substrate side with a metal halide lamp, followed by light irradiation from the counter electrode substrate side.
- a plurality of connecting members arranged in the substrate after bonding are cut out, and conductive copper foils are formed on the wirings arranged at both ends (extracting electrode portions) of each connecting member.
- a tape (CU7636D, manufactured by Sony Chemical & Information Device Co., Ltd., copper foil thickness as a conductor: 35 ⁇ m) was attached.
- the surface of the conductive copper foil tape used in this example is previously coated with a conductive adhesive made of a conductive acrylic resin. Therefore, the electrical connection portion interposed between the photoelectrode / counter electrode and the extraction electrode is formed by a conductive adhesive coated on the conductor forming the extraction electrode.
- the conductive copper foil tape for forming the extraction electrode prior to attachment, the conductive portion of the portion other than the region used for attachment to the photoelectrode / counter electrode (that is, the region for forming the electrical connection portion) is used. What removed the coating of the adhesive was used. Next, two barrier films (Neo Seeds, “Ultra High Barrier Film”, water vapor transmission rate: 0.00005 g / m 2 / day), which is a barrier packaging material larger than the above connection body, were prepared.
- One of the barrier films is fixed on an aluminum suction plate using a vacuum pump, and a filling member is formed at a position where it overlaps the wiring of the extraction electrode when the connection body is stacked with the counter electrode facing down
- a resin composition (“TB3035B”, UV curable acrylic resin, manufactured by Three Bond Co., Ltd.) was applied. Therefore, the surface of the connecting body on the counter electrode side and the barrier film were not bonded. On top of that, the connection body was stacked so that the conductive copper foil tape was taken out of the barrier film, and light was irradiated from the barrier film side.
- Another barrier film and the upper member of the pressing member are stacked from above, and after pressing the connection body in the thickness direction, light irradiation is performed and the exterior is covered with the barrier film.
- a dye-sensitized solar cell module extended from is obtained.
- the retention rate of the obtained solar cell module was measured according to the above method and found to be 95%.
- Example 2 The same dye solution preparation step and photoelectrode substrate preparation step as in Example 1 were performed. And in the manufacturing process of the solar cell module, the connection body was formed and cut out in the same manner as in Example 1, and the solar cell module was formed in the following manner for each subsequent process.
- a resin frame-shaped molded body for example, FIG. 3 and FIG. A frame-shaped molded body 31 shown in 4 was prepared.
- Such a frame-shaped molded body is a light-transmitting resin molded body, and is formed using a resin composition (manufactured by Nippon Zeon, “Zeonex”).
- a resin composition similar to that applied to the bottom is applied to the region where the extraction electrode on the inner side surface of the frame-shaped molded body should be extended, and the copper foil other than the portion adhered to the bottom is applied to the frame-shaped molded body. It was bent along the shape and irradiated with light from the frame-shaped molded body side to cure the resin composition, thereby bonding the frame-shaped molded body and the copper foil. Further, conductive paste Dotite (registered trademark) (“Dotite D-362” manufactured by Fujikura Kasei Co., Ltd.) is brought into contact with the side surface of the connection body and the inner surface of the frame-shaped molded body at a position overlapping the wiring at the end of the connection body.
- Dotite registered trademark
- Dotite D-362 manufactured by Fujikura Kasei Co., Ltd.
- a resin composition manufactured by ThreeBond, “TB3035B”, an ultraviolet curable acrylic resin
- the connection body is fitted to the inner frame portion of the frame-shaped molded body to solidify the dotite at room temperature, and the resin composition is cured by irradiating light from the frame-shaped molded body side.
- a body fitting body was produced.
- a barrier film as a barrier packaging material having a size smaller than the outer frame of the frame-shaped molded body (Neo Seeds, “Ultra High Barrier Film”, water vapor transmission rate: 0.
- a barrier film as a barrier wrapping material of a size capable of covering at least the entire upper surface of the fitting body is adhered to the opposite surface of the solar cell module via a similar resin composition, and the takeout electrode Obtained a dye-sensitized solar cell module exposed at the bottom of the module. It was 94% when the retention rate of the obtained solar cell module was measured according to the said method.
- Example 3 A resin frame-like molded body similar to that in Example 2 was used. At this time, the frame-shaped molded body was masked in such a manner as to expose the region where the copper foil was adhered in Example 2, and titanium, which is a conductive material, was deposited on the exposed surface. .
- a dye-sensitized solar cell module in which the extraction electrode was exposed on the bottom surface of the module was produced in the same manner as in Example 2 except that the frame-shaped molded body with a conductive layer thus formed was used. Therefore, the process similar to Example 2 was performed except the process of attaching copper foil with respect to a frame-shaped molded object. It was 97% when the retention rate of the obtained solar cell module was measured according to the said method.
- Example 4 instead of the frame-shaped molded body formed from the resin composition of Example 2, an aluminum frame-shaped molded body having the same shape was formed by cutting, and the entire surface was subjected to insulating coating with high-density polyethylene. In the same manner as in Example 2, the copper foil was attached to the region where the copper foil was attached in Example 2 to the frame-shaped molded body thus prepared. However, instead of TB3035B, a delayed curable adhesive was used as the resin composition, a copper foil was disposed after the adhesive was applied, and heated in an oven at 100 ° C. A fitting body of the connection body and the frame-shaped molded body was prepared in the same manner as in Example 2.
- a delayed curable adhesive was used as the resin composition, fitting was performed after the adhesive was applied, and heating was performed in an oven at 60 ° C. Other than that was carried out similarly to Example 2, and obtained the dye-sensitized solar cell module by which an extraction electrode is exposed to the bottom face of a module. The retention rate of the obtained solar cell module was measured according to the above method and found to be 99%.
- Example 5 A pair of aluminum frame-shaped molded bodies 32 having a shape as shown in FIG. 5 was produced by cutting.
- the frame-shaped molded body 32 includes a first frame-shaped molded body unit 32A and a second frame-shaped molded body unit 32B.
- the first frame-shaped molded body unit 32A and the second frame-shaped molded body unit 32B were joined, the same shape as the frame-shaped molded body of Example 2 was obtained. That is, the pair of frame-shaped molded bodies 32 has a shape corresponding to the shape obtained by dividing the frame-shaped molded body of Example 2 into two when the first and second extraction electrodes are viewed on the left and right.
- the insulation coating by a high-density polyethylene resin was given to the joint surface 33 of 32 A of 1st frame-shaped molded object units and the 2nd frame-shaped molded object unit 32B. Further, after applying a delayed curable adhesive to one of the first and second frame-shaped molded body units 32A and 32B in which the bonding surface 33 is resin-coated, and after light irradiation, Joined to the other unit and heated in an oven at 100 ° C., a conductive surface exposed frame-shaped molded body 32 in which aluminum forming the conductive surface was exposed on the surface was produced.
- a dye-sensitized solar cell module in which the extraction electrode was exposed on the bottom surface of the module was produced in the same manner as in Example 4 except that the conductive surface exposed frame-shaped molded body 32 thus formed was used. It was 98% when the retention rate of the obtained solar cell module was measured according to the said method.
- connection body is stacked with the counter electrode side facing down without applying the resin composition for forming the filling member to the barrier film fixed on the aluminum adsorption plate. It was. Except this, it carried out similarly to Example 1, and produced the dye-sensitized solar cell module in which the extraction electrode extended from the side of the module. In the obtained dye-sensitized solar cell module, it was visually confirmed that there was a space between the extraction electrode and the barrier film. Moreover, it was 32% when the retention rate of the obtained solar cell module was measured according to the said method.
- the solar cell module in which the filling member is present in at least a part of the gap in the substrate surface direction between the outer periphery of the connection body and the barrier packaging material is It can be seen that the conversion efficiency retention rate is excellent. Moreover, it turns out from the comparative example 1 that the solar cell module in which a filling member does not exist in this gap is inferior in photoelectric conversion retention.
- a solar cell module that has a barrier packaging material that protects the solar cell module from the external environment and that has an excellent photoelectric conversion efficiency retention rate.
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Abstract
Description
そこで、本発明は、太陽電池モジュールを外部環境の変動から保護するバリア包装材を有する、光電変換効率の保持率に優れる、太陽電池モジュールを提供することを目的とする。
ここで、本明細書において、「枠状」とは、少なくとも外縁と内縁を有する形状を意味する。これらの外縁又は内縁の形状は特に限定されることなく、例えば、矩形、多角形、円形、楕円、及びその他のあらゆる形状でありうる。
充填部材が枠状成形体を含むことで、枠状成形体が含まれない場合と比較して、封止部周辺が湾曲しにくくなるため応力の発生が抑制されてバリア包装材が剥離しにくくなる効果が見込まれる。さらに、枠状成形体の厚みを太陽電池モジュールの厚みと合わせることで、太陽電池モジュールにおけるバリア包装材封止部領域とそれ以外の領域で段差が生じないため、太陽電池モジュールを他の部材と組み合わせるといった後工程においても、取扱い性が向上する。
ここで、図1及び図2に示す太陽電池モジュール100の第1基板3は、第1基材1と、第1基材1上に互いに離隔させて設けられた複数の光電極2とを備えている。また、光電極2は、第1基材1上に設けられた光電極用導電層21と、光電極用導電層21上の一部に設けられた多孔質半導体微粒子層22とを備えている。なお、光電極用導電層21は、隙間をあけて設けられている。そして、互いに隣接する光電極2同士は、互いに電気的に絶縁されるように設けられている。この絶縁は、特に限定されることなく、例えば互いに隣接する光電極用導電層21間の隙間に存在する隔壁8によって達成することができる。
なお、第1基材1上に光電極用導電層21を形成する方法としては、スパッタリングとエッチングとを組み合わせた方法や、スクリーン印刷など、既知の形成方法を用いることができる。
下塗り層は、内部短絡現象を防ぐことのできる(界面反応が起こりにくい)物質であれば、特に限定はされない。例えば、酸化チタン、酸化ニオブ、酸化タングステン等の材料を含んでなる層でありうる。また、下塗り層を形成する方法としては、上記材料を透明導電層に直接スパッタする方法、あるいは上記材料を溶媒に溶解した溶液、金属酸化物の前駆体である金属水酸化物を溶解した溶液、又は有機金属化合物を、水を含む混合溶媒に対して溶解して得た金属水酸化物を含む溶液を、光電極用導電層21上に塗布、乾燥し、必要に応じて焼結する方法がある。
また、太陽電池モジュール100の第2基板7は、第2基材5と、第2基材5上に互いに離隔させて設けられた複数の対向電極6とを備えている。また、対向電極6は、第2基材5上に設けられた対向電極用導電層61と、対向電極用導電層61上の一部に設けられた触媒層62とを備えている。なお、対向電極用導電層61は、隙間をあけて設けられている。そして、触媒層62は、光電極2の多孔質半導体微粒子層22に対向している。
なお、互いに隣接する対向電極6同士は、互いに電気的に絶縁されるように設けられている。この絶縁は、特に限定されることなく、例えば互いに隣接する対向電極6間の隙間に隔壁8を介在させることにより、達成することができる。
ここで、導電性高分子としては、例えば、ポリ(チオフェン-2,5-ジイル)、ポリ(3-ブチルチオフェン-2,5-ジイル)、ポリ(3-ヘキシルチオフェン-2,5-ジイル)、ポリ(2,3-ジヒドロチエノ-[3,4-b]-1,4-ジオキシン)(PEDOT)等のポリチオフェン;ポリアセチレンおよびその誘導体;ポリアニリンおよびその誘導体;ポリピロールおよびその誘導体;ポリ(p-キシレンテトラヒドロチオフェニウムクロライド)、ポリ[(2-メトキシ-5-(2’-エチルヘキシロキシ))-1,4-フェニレンビニレン]、ポリ[(2-メトキシ-5-(3’,7’-ジメチルオクチロキシ)-1,4-フェニレンビニレン)]、ポリ[2-2’,5’-ビス(2’’-エチルヘキシロキシ)フェニル]-1,4-フェニレンビニレン]等のポリフェニレンビニレン類;などを挙げることができる。
炭素ナノ構造体としては、例えば、天然黒鉛、活性炭、人造黒鉛、グラフェン、カーボンナノチューブ、カーボンナノバッドなどを挙げることができる。
貴金属としては、触媒作用のあるものであれば特に限定されず、金属白金、金属パラジウム、及び金属ルテニウムなどの公知の貴金属を適宜選択して用いることができる。
なお、製造容易性の観点から、上述したような各種樹脂がシート状に成形されてなるフィルムを用いて、隔壁8を構成することももちろん可能である。
また、太陽電池モジュール100の機能層である電解質層4は、光電極2の多孔質半導体微粒子層22と、対向電極6の触媒層62と、隔壁8とで囲まれる空間に設けられている。そして、電解質層4は、特に限定されることなく、色素増感型太陽電池において使用し得る任意の電解液、ゲル状電解質又は固体電解質を用いて形成することができる。
太陽電池モジュール100のセル接続部9は、互いに隣接するセルを電気的に直列接続している。具体的には、セル接続部9は、図2では右側に位置するセルの光電極2の光電極用導電層21と、図2では左側に位置するセルの対向電極6の対向電極用導電層61とを電気的に接続している。
そして、導電性粒子の平均粒子径は、0.5μm以上30μm以下であることが好ましい。更に、導電性粒子の含有割合は、0.1体積%以上90体積%以下であることが好ましい。
そして、光電極2と対向電極6に対して、それぞれ接続された、第1取り出し電極11A及び第2取り出し電極11Bは、特に限定されることなく、一般的な導電性材料により形成された導体を有する。そのような導体としては、銅、アルミニウム、ニッケル、チタン、及び鉄等からなる群から選ばれる金属材料、及びこれらの金属材料を含む合金材料により形成された導体が挙げられる。中でも、銅を導体とする電極或いは、ステンレスを基材とするものが好ましい。
封止部14は、硬化状態の封止部用樹脂組成物15により封止されている。封止部用樹脂組成物としては、特に限定されることなく、光硬化性樹脂組成物、熱硬化型樹脂組成物、及び熱可塑性樹脂組成物を挙げることができる。中でも、封止部用樹脂組成物としては、光硬化性樹脂組成物を用いることが好ましい。封止部用樹脂組成物が光硬化性であれば、特に有機系太陽電池の製造工程における加熱による劣化を予防して太陽電池モジュールの電気的特性を向上させることができる。さらに、光硬化性樹脂は短時間で硬化可能であるため、製造効率の良好な太陽電池モジュールを得ることが期待できる。
光硬化性樹脂組成物としては、紫外線硬化型樹脂組成物、及び可視光硬化性樹脂組成物が挙げられるが、紫外線硬化型樹脂組成物を用いることが好ましい。紫外線硬化型樹脂組成物の具体例としては、(メタ)アクリル系樹脂組成物、エポキシ系樹脂組成物、フッ素系樹脂組成物、オレフィン系樹脂組成物等が挙げられるが、なかでも、アクリル系樹脂組成物、エポキシ系樹脂組成物、又はフッ素系樹脂組成物を用いることが好ましい。これらは1種類のみを単独で、或いは2種類以上を混合して用いてもよい。
熱硬化型樹脂組成物としては、電解質層4を構成する電解質を気化させない温度で硬化可能な熱硬化型樹脂組成物が挙げられる。より具体的には、硬化温度が60℃~200℃の範囲内、なかでも80℃~180℃の範囲内、さらには100℃~160℃の範囲内である熱硬化型樹脂組成物が挙げられる。熱硬化型樹脂組成物の具体例としては、例えば、(メタ)アクリル系樹脂組成物、エポキシ系樹脂組成物、フッ素系樹脂組成物、シリコーン系樹脂組成物、オレフィン系樹脂組成物、ポリイソブチレン樹脂組成物等が挙げられる。これらは1種類のみを単独で、或いは2種類以上を混合して用いてもよい。
熱可塑性樹脂組成物としては、電解質層中の液体を気化させない程度の温度を融点とする熱可塑性樹脂が挙げられる。より具体的には、融点が80℃~250℃の範囲内、なかでも100℃~200℃の範囲内である熱可塑性樹脂が挙げられる。熱可塑性樹脂の具体例としては、例えば、オレフィン系樹脂、ポリイソブチレン樹脂、シリコーン系樹脂、(メタ)アクリル系樹脂、ポリアミド樹脂等が挙げられる。これらは1種類のみを単独で、或いは2種類以上を混合して用いてもよい。
また、封止部14は、同一又は異なる素材よりなる複数部材により構成されうる。例えば、封止部14は、金属又は樹脂よりなる封止部材と、かかる封止部材と上下のバリア包装材13A及び13Bとを接着する硬化された封止部用樹脂組成物より構成されうる。
そして、バリア包装材13A及び13Bは、太陽電池モジュール100が曝されうる高温や高湿度の環境条件下で、太陽電池モジュール100に対して耐久性を付与する。従って、バリア包装材13A及び13Bは、ガスや水蒸気に対するバリア性のある包装体であることが好ましい。さらに、図2では、バリア包装材として、2枚のバリア包装材13A及び13Bを図示する。図2から明らかなように、バリア包装材13Aは第1基板3側に配置されており、バリア包装材13Bは第2基板7側に配置されている。しかし、バリア包装材は図2に示したような太陽電池モジュールの厚み方向上下にそれぞれ配置された2枚のシート状の包装体であることには限定されず、薄板状であっても良く、さらには、太陽電池モジュールを構成する複数のセルの奥行き方向(図2では左右方向)で開放している筒状のフィルムであっても良い。
また、特に、太陽電池モジュールが色素増感型太陽電池モジュールの場合には、用いる色素の吸収波長域における光の透過率が高い材料を接着層の形成材料として選択することが好ましい。
さらに、バリア包装材13A及び13Bは、全光線透過率が好ましくは50%以上、より好ましくは70%以上、更に好ましくは85%以上である。このような全光線透過率は、例えばJIS K7361-1により測定することができる。
また、後述するように、特に枠状成形体31とバリア包装材13A又は13Bを一体で成形する場合は、一体成型体において、バリア包装材はフィルム形状であっても、薄板形状であっても構わない。
複数のセルの接続体の外周(より具体的には、図2に示す例では、複数のセルに備えられた隔壁8)と、バリア包装材13Bとの間における、基板面方向の間隙内の少なくとも一部には、充填部材30が存在する。充填部材30は、上記間隙内で、接続体の外周に接触してなることが好ましい。さらに、充填部材30は、上記間隙の全体積の90%以上を占有することが好ましく、95%以上を占有することがより好ましく、99%以上を占有することが更に好ましい。上記間隙内にて気体の占有しうる体積を抑制することで、太陽電池モジュールが温度上昇した際に気体が膨張して封止部14に剥離を生じさせることを抑制できるからである。さらに、充填部材30は、硬化された樹脂組成物、及び/又は、内側面形状の少なくとも一部が複数のセルの接続体の側面に沿う枠状成形体を含みうる。枠状成形体は、例えば、図3に示す枠状成形体31のような形状でありうる。充填部材が枠状成形体31を含むことで、枠状成形体31が含まれない場合と比較して、封止部周辺が湾曲しにくくなるため応力の発生が抑制されてバリア包装材13A及び13Bが剥離しにくくなる効果が見込まれる。さらに、枠状成形体31の厚みを太陽電池モジュール100の厚みと合わせることで、太陽電池モジュールにおけるバリア包装材封止部領域とそれ以外の領域で段差が生じないため、太陽電池モジュールを他の部材と組み合わせるといった後工程においても、取扱い性が向上する。
更に、枠状成形体は、バリア包装材封止部よりも透湿性が抑制されていることが好ましい。透湿性を抑制する方法としては、枠状成形体自体の透湿性を低くする方法、或いは枠状成形体の表面などの少なくとも一部に透湿性の低い金属材料層などを形成するなどの方法がある。枠状成形体31を封止部の一部として機能させる態様では、見かけ上バリア包装材13A及び13Bの間の距離が広がるが、太陽電池モジュール100内部への透湿を抑制することができる。なお、枠状成形体に金属等の導電性材料を用いる場合、太陽電池モジュールへの実装に際して絶縁が必要となる個所には、コーティング等で適宜絶縁部を形成する。
また、枠状成形体が樹脂材料からなる場合、導体は、枠状成形体31の表面上に配置される形態のみでなく、枠状成形体31の内部に形成される形態であってもよい。この場合、例えば枠状成形体31に予め貫通部を作製し、そこにはんだや導電性樹脂等を充填することで、枠状成形体31の内部を貫通する導体を形成できる。
また、枠状成形体31が導電性材料からなる場合、表面を絶縁性の樹脂等で被覆し、部分的に露出した導電面を、第1取り出し電極11A及び第2取り出し電極11Bとしてもよい。
上述した構成を有する太陽電池モジュール100は、特に限定されることなく、例えば、以下のような手順により製造することができる。具体的にはまず、光電極2を備える第1基板3を作製した後、作製した第1基板3の上に、配線91を形成する。次に、配線91に重なる位置に、未硬化の導電性樹脂組成物92を塗布し、さらに塗布した導電性樹脂組成物92を挟んでそれぞれ光電極用導電層21を囲むように隔壁材料を塗布する。そして、隔壁材料を塗布した領域内に電解液などの電解質層4を構成する成分を充填する。その後、対向電極6を備える第2基板7を、第1基板3と重ね合わせる。さらに、未硬化の導電性樹脂組成物92を硬化させてセル接続部9を形成すると共に第1基板3と第2基板7とを強固に接着させて、一対の電極基板を含む複数セルの接続体を得る。
なお、上記図3及び図4を参照して説明した構造を有する太陽電池モジュール101を製造する際には、まず、枠状成形体31を準備する。ここで、枠状成形体31は、導電性材料を用いた表面処理により形成された導電層を有していても良い。枠状成形体31は、所望形状を有する金型内に上述したような樹脂組成物を流し込み硬化させることで形成することができる。そして、得られた枠状成形体31に対して、樹脂組成物を介して取り出し電極11A及び11Bを取り付ける。そして、枠状成形体31、取り出し電極11A/11Bと、バリア包装材13A及び13Bとを、樹脂組成物を介して密着させて、上記図3及び図4を参照して説明した構造を有する太陽電池モジュール101を得ることができる。
実施例および比較例において、封止部における剥離の発生の有無、及び太陽電池モジュールの保持率は以下の方法を使用して測定した。
実施例、比較例で得られた太陽電池モジュールを目視観察して、封止部においてバリアフィルムの剥離が生じているか否かを下記基準に従って判定した。
剥離有:封止部端部に剥離が発生
剥離無:封止部全周の封止幅の90%以上で剥離無し
<太陽電池モジュールの保持率>
実施例、比較例で作製した太陽電池モジュールをソースメータ(2400型ソースメータ、Keithley社製)に接続した。光源としては、150Wキセノンランプ光源装置にAM1.5Gフィルタを装着した擬似太陽光源(PEC-L11型、ペクセル・テクノロジーズ(株)製)を用いた。そして、光源の光量を、1sun(約10万lux AM1.5G、100mWcm-2(JIS C 8912のクラスA))に調整して、太陽電池モジュールに対して照射した。太陽電池モジュールについて、1sunの光照射下、バイアス電圧を、0Vから0.8Vまで、0.01V単位で変化させながら出力電流を測定し、電流電圧特性を取得した。同様に、バイアス電圧を、逆方向に0.8Vから0Vまでステップさせる測定も行い、順方向と逆方向の測定の平均値を光電流データとした。このようにして得られた電流電圧特性及び光電流データより、初期の光電変換効率(%)を算出した。
次いで、上記の色素増感太陽電池モジュールを、65℃90%RHの環境に300時間保持した後、上記と同様に電流電圧特性を測定した。上記と同様にして変換効率を求め、下式に従って初期の値に対する保持率を計算した。[保持率(%)]=[65℃90%RH保持後の変換効率]/[初期の変換効率]×100
<色素溶液の調製>
ルテニウム錯体色素(N719、ソラロニクス社製)72mgを200mLのメスフラスコに入れた。脱水エタノール190mLを混合し、撹拌した。メスフラスコに栓をしたのち超音波洗浄器による振動により、60分間撹拌した。溶液を常温に保った後、脱水エタノールを加え、全量を200mLとすることで、色素溶液を調製した。
<光電極基板の作製>
光電極用基材である透明基板(ポリエチレンナフタレートフィルム、厚み200μm)上に光電極用導電層である透明導電層(酸化インジウムスズ(ITO))をコートして得た透明導電性基板(シート抵抗13ohm/sq)上に、スクリーン印刷法により配線(集電線)としての導電性銀ペースト(K3105、ペルノックス(株)製)を光電極セル幅に応じた間隔で印刷塗布し、150度の熱風循環型オーブン中で15分間加熱乾燥して配線を作製した。得られた配線を有する透明導電性基板を、配線形成面を上にして塗布コーターにセットし、1.6%に希釈したオルガチックPC-600溶液(マツモトファインケミカル製)をワイヤーバーにより掃引速度(10mm/秒)で塗布した。得られた塗膜を、10分間室温乾燥した後、さらに10分間150℃で加熱乾燥して、透明導電性基板上に下塗り層を作製した。
透明導電性基板の下塗り層形成面に対して、光電極セル幅に応じた間隔でレーザー処理を行い、絶縁線を形成した。
そして、ポリエステルフィルムに粘着層を塗工した保護フィルムを2段重ねして得たマスクフィルム(下段:PC-542PA 藤森工業製、上段:NBO-0424 藤森工業製)に、多孔質半導体微粒子層を形成するための開口部(長さ:60mm、幅5mm)を打ち抜き加工した。加工済みマスクフィルムを、気泡が入らないように、下塗り層を形成した透明導電性基板の集電線形成面に貼合した。なお、マスクフィルムの一層目は色素の不要箇所への付着防止を目的としたものであり、二層目は多孔質半導体微粒子の不要箇所への付着防止を目的としたものである。
高圧水銀ランプ(定格ランプ電力 400W)光源をマスク貼合面から10cmの距離に置き、電磁波を1分間照射した後直ちに、酸化チタンペースト(PECC-C01-06、ペクセル・テクノロジーズ(株)製)をベーカー式アプリケータにより塗布した。ペーストを常温で10分間乾燥させた後、マスクフィルムの上側の保護フィルム(NBO-0424 藤森工業製)を剥離除去し、150度の熱風循環式オーブン中でさらに5分間加熱乾燥し、多孔質半導体微粒子層(長さ:60mm、幅5mm)を形成した。
その後、多孔質半導体微粒子層(長さ:60mm、幅5mm)を形成した透明導電性基板を、調製した色素溶液(40℃)に浸し、軽く攪拌しながら、色素を吸着させた。90分後、色素吸着済み酸化チタン膜を色素吸着容器から取り出し、エタノールにて洗浄して乾燥させ、残りのマスクフィルムを剥離除去して、光電極を作製した。
<対向電極基板の作製>
対向電極用基材である透明基板(ポリエチレンナフタレートフィルム、厚み200μm)上に対向電極用導電層である透明導電層(酸化インジウムスズ(ITO))をコートして得た透明導電性基板(シート抵抗13ohm/sq.)の導電面に、白金膜パターン幅に応じた間隔でレーザー処理を行い、絶縁線を形成した。次いで、開口部(長さ:60mm、幅5mm)を打ち抜き加工した金属製マスクを重ね合わせ、スパッタ法により白金膜パターン(触媒層)を6つ形成し、触媒層形成部分が72%程度の光透過率を有する対向電極基板を得た。このとき、上記光電極基板と対向電極基板とを、お互いの導電面を向かい合わせて重ね合せた時、多孔質半導体微粒子層と触媒層とが一致する構造とした。
<色素増感太陽電池モジュールの作製>
導電性樹脂組成物の樹脂材料であるアクリル系樹脂としてのTB3035Bに対して、積水樹脂製ミクロパールAU(粒子径8μm)を、3質量%になるように添加して、自転公転ミキサーにより均一に混合し、導電性樹脂組成物を作製した。
対向電極基板の触媒層形成面を表面として、アルミ製吸着板上に真空ポンプを使って固定した。次いで触媒層間の、光電極基板と対向させたときに光電極セル間の配線と重なる位置に線状に導電性樹脂組成物を、その線を挟み触媒層の外周部分に隔壁材料である液状の紫外線硬化型封止剤TB3035B((株)スリーボンド製、吸収波長:200nm~420nm)を、ディスペンサー装置により塗布した。その後、触媒層部分に電解液を所定量塗布し、自動貼り合せ装置を用いて長方形の触媒層と同型の多孔質半導体微粒子層が向かい合う構造となるように、減圧環境中で重ね合せ、光電極基板側からメタルハライドランプにより光照射を行い、続いて対向電極基板側から光照射を行った。その後、貼り合せ後の基板内に配置された複数個の接続体を各々切出し、各接続体の両端部(取り出し電極部)に配置された配線に対して、取出し電極を形成する導電性銅箔テープ(CU7636D、ソニーケミカル&インフォメーションデバイス(株)製、導体である銅箔の厚み:35μm)を取り付けた。ここで、本実施例で用いた導電性銅箔テープは、表面が導電性アクリル樹脂よりなる導電性粘着剤により予めコーティングされている。そのため、光電極/対向電極と、取り出し電極との間に介在する電気的接続部は、取出し電極を形成する導体上にコーティングされた導電性粘着剤により形成される。さらに、取出し電極を形成する導電性銅箔テープとしては、取り付けに先立って、光電極/対向電極に対する取り付けに使用する領域(すなわち、電気的接続部を形成するための領域)以外の部分の導電性粘着剤のコーティングを除去したものを用いた。
次いで、上記接続体より大きいバリア包装材であるバリアフィルム(ネオシーズ社、「ウルトラハイバリアフィルム」、水蒸気透過度:0.00005g/m2/日)を2枚準備した。そのうちの1枚のバリアフィルムを、アルミ製吸着板上に真空ポンプを使って固定し、接続体を対向電極側を下にして重ねたとき取出し電極部の配線と重なる位置に、充填部材を形成するための樹脂組成物(スリーボンド社製、「TB3035B」、紫外線硬化型アクリル系樹脂)を塗布した。よって、対向電極側の接続体表面とバリアフィルムとは接着しなかった。
その上に上記導電性銅箔テープがバリアフィルム外に取り出されるように接続体を重ね、バリアフィルム側から光照射した。そして、接続体の表面全体と、その外周部の上記導電性銅箔テープ表面(コーティング除去済み)を含むバリアフィルム上と、外周部の導電性銅箔テープの裏面に封止部を形成するための樹脂組成物である液状の樹脂組成物(スリーボンド社製、「TB3035B」、紫外線硬化型アクリル系樹脂)を塗布した。
そして、光電極基板及び対向電極基板の外周部近辺にそれぞれ当接する部分が突出したゴム材料からなる突出面を有する治具である上下一対の押圧部材の、下側部材上にバリアフィルムにより挟まれた色素増感太陽電池モジュールを載置した。続いて、上から、もう一枚のバリアフィルム、及び上記押圧部材の上側部材を重ね、接続体を厚み方向に加圧後、光照射を行い、バリアフィルムで外装し、取り出し電極がモジュールの横から延出してなる色素増感太陽電池モジュールを得た。
得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、95%であった。
実施例1と同様の色素溶液の調製工程、光電極基板の作製工程を行った。そして、太陽電池モジュールの作製工程では、実施例1と同様にして接続体を形成して切り出し、それ以降の各工程については以下のようにして、太陽電池モジュールを形成した。
なお、本実施例では、各工程に先立って、まず、充填部材として、内側面形状の少なくとも一部が複数のセルの接続体の側面に沿う樹脂製枠状成形体(例えば、図3及び図4に示す枠状成形体31)を準備した。かかる枠状成形体は、光透過性の樹脂成形体であり、樹脂組成物(日本ゼオン製、「ゼオネックス」)を用いて形成されてなる。
そして、実施例1に示した太陽電池モジュールの作製工程において、接続体の両端部に配置された配線に対して銅箔テープを貼る工程を省略した。かかる工程に代えて、本実施例では、枠状成形体の底部の取り出し電極を延在させるべき領域に樹脂組成物(スリーボンド社製、「TB3035B」、紫外線硬化型アクリル系樹脂)を塗布した。そして、枠状成形体底部の塗布面に対して銅箔を張り付けて、枠状成形体側から光照射を行い、樹脂組成物を硬化させて枠状成形体と銅箔とを接着させた。さらに、枠状成形体の内側側面の取り出し電極を延在させるべき領域に底部に塗布したものと同様の樹脂組成物を塗布し、底部に接着された部分以外の銅箔を枠状成形体の形状に沿わせて折り曲げ、枠状成形体側から光照射を行い、樹脂組成物を硬化させて枠状成形体と銅箔とを接着させた。
さらに、接続体端部の配線と重なる位置に導電性ペーストドータイト(登録商標)(藤倉化成製、「ドータイトD-362」)を、接続体の側面と枠状成形体の内側面とが接触する部分には樹脂組成物(スリーボンド社製、「TB3035B」、紫外線硬化型アクリル系樹脂)を、それぞれ塗布した。ここに、接続体を枠状成形体の内枠部分に嵌合させて室温にてドータイトを固化させるとともに、枠状成形体側から光照射して樹脂組成物を硬化させ、接続体と枠状成形体の嵌合体を作製した。続いて、色素増感太陽電池モジュールの作製工程にて、枠状成形体の外枠よりも小さいサイズのバリア包装材としてのバリアフィルム(ネオシーズ社、「ウルトラハイバリアフィルム」、水蒸気透過度:0.00005g/m2/日)をアルミ製吸着板上に固定し、全面に樹脂組成物(スリーボンド社製、「TB3035B」、紫外線硬化型アクリル系樹脂)を塗布した。そして、銅箔を有する嵌合体の底面を上から重ねて、バリアフィルム側から光照射を行って封止した。このとき、嵌合体底面上の銅箔のうちの一部が、太陽電池モジュール外に露出するため、取り出し電極として機能するようになる。さらに、太陽電池モジュールの反対側の面に対して、少なくとも嵌合体の上面の全体を被覆しうるサイズのバリア包装材としてのバリアフィルムを、同様の樹脂組成物を介して接着させて、取り出し電極がモジュールの底面に露出してなる色素増感太陽電池モジュールを得た。
得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、94%であった。
実施例2と同様の樹脂製枠状成形体を用いた。この際、枠状成形体に対して、実施例2にて銅箔を張り付けた領域を露出させるような態様でマスキングを施し、露出した表面に対して、導電性材料であるチタンを蒸着させた。このようにして形成した導電層付き枠状成形体を用いた以外は実施例2と同様にして、取り出し電極がモジュールの底面に露出してなる色素増感太陽電池モジュールを作製した。
従って、銅箔を枠状成形体に対して取り付ける工程以外は実施例2と同様の工程を行った。得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、97%であった。
実施例2の樹脂組成物から形成される枠状成形体に替えて、同形状のアルミニウム製の枠状成形体を切削により作成し、表面全体に高密度ポリエチレンによる絶縁コーティングを行った。このようにして作成した枠状成形体に対して、実施例2にて銅箔を貼りつけた領域に、実施例2と同様にして銅箔を貼りつけた。ただし、樹脂組成物としては、TB3035Bに替えて、遅延硬化型接着剤を用い、接着剤の塗布後に銅箔を配置し、100℃のオーブン内で加熱した。接続体と枠状成形体の嵌合体も実施例2と同様にして作成した。ただし、樹脂組成物としては、TB3035Bに替えて、遅延硬化型接着剤を用い、接着剤の塗布後に嵌合を行い、60℃のオーブン内で加熱した。それ以外は実施例2と同様にして、取り出し電極がモジュールの底面に露出してなる色素増感太陽電池モジュールを得た。得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、99%であった。
図5に示すような形状の一対のアルミニウム製の枠状成形体32を切削により作製した。枠状成形体32は、第1枠状成形体ユニット32Aと第2枠状成形体ユニット32Bよりなる。第1枠状成形体ユニット32Aと第2枠状成形体ユニット32Bを接合すると実施例2の枠状成形体と同形状となるようにした。すなわち、一対の枠状成形体32は実施例2の枠状成形体を第1及び第2取り出し電極を左右にみて2分割した形状に相当する形状とした。そして、第1枠状成形体ユニット32Aと第2枠状成形体ユニット32Bの接合面33には、高密度ポリエチレン樹脂による絶縁コーティングを施した。さらに、接合面33を樹脂被覆した第1枠状成形体ユニット32A及び第2枠状成形体ユニット32Bの何れか一方の接合面33に遅延硬化型接着剤を塗布し、光照射をした後もう他方のユニットと接合し、100℃のオーブン内で加熱して、導電面を形成するアルミニウムが表面に露出した導電面露出枠状成形体32を作製した。このようにして形成した導電面露出枠状成形体32を用いた以外は実施例4と同様にして、取り出し電極がモジュールの底面に露出してなる色素増感太陽電池モジュールを作製した。得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、98%であった。
さらに、太陽電池モジュール作製工程において、アルミ製吸着板上に固定したバリアフィルムに対して、充填部材を形成するための樹脂組成物を塗布することなく、対向電極側を下にして接続体を重ねた。これ以外は、実施例1と同様にして、取り出し電極がモジュールの横から延出してなる色素増感太陽電池モジュールを作製した。
得られた色素増感太陽電池モジュールにおいて、取出し電極とバリアフィルムとの間に空間があることを目視で確認した。また、得られた太陽電池モジュールの保持率を上記方法に従って測定したところ、32%であった。
2 光電極
3 第1基板
4 電解質層
5 第2基材
6 対向電極
7 第2基板
8 隔壁
9 セル接続部
11A 第1取り出し電極
11B 第2取り出し電極
12A 第1電気的接続部
12B 第2電気的接続部
13A,13B バリア包装材
14 封止部
15 硬化状態の封止部用樹脂組成物
21 光電極用導電層
22 多孔質半導体微粒子層
30 充填部材
31 枠状成形体
32 導電面露出枠状成形体
61 対向電極用導電層
62 触媒層
91 配線
92 導電性樹脂組成物
100,101 太陽電池モジュール
Claims (9)
- 第1基板側の第1電極と、第2基板側の第2電極とが、機能層を介して対向してなる1つまたは複数の光電変換セルを含む接続体と、
封止部により封止されて、前記接続体を包含する少なくとも1つのバリア包装材と、
前記第1電極に第1電気的接続部を介して接続する第1取り出し電極、及び前記第2電極に第2電気的接続部を介して接続する第2取り出し電極とを備える太陽電池モジュールであって、
前記太陽電池モジュールは、前記接続体の外周と前記バリア包装材との間に、前記第1基板の面方向及び前記第2基板の面方向を含む基板面方向で、間隙を有し、前記間隙内の少なくとも一部に、充填部材が存在する、
太陽電池モジュール。 - 前記充填部材が、硬化された樹脂組成物を含む、請求項1に記載の太陽電池モジュール。
- 前記封止部の少なくとも一部が前記充填部材と一体である、請求項1又は2に記載の太陽電池モジュール。
- 前記充填部材が、
内側面形状の少なくとも一部が前記接続体の側面に沿う枠状成形体を含む、請求項3に記載の太陽電池モジュール。 - 前記枠状成形体が前記バリア包装材の一部と一体である、請求項4に記載の太陽電池モジュール。
- 前記枠状成形体が少なくとも一つの導体あるいは部分的な導電層を有し、該少なくとも一つの導体あるいは部分的な導電層が、前記第1又は第2取り出し電極として機能し、且つ、
前記導体あるいは部分的な導電層の少なくとも一部が、前記バリア包装材により被覆されていない、請求項4又は5に記載の太陽電池モジュール。 - 前記導電層が、導電性材料を用いた表面処理により前記枠状成形体上に形成された導電層である、請求項6に記載の太陽電池モジュール。
- 前記第1基板及び/又は第2基板と、前記バリア包装材との間隙の少なくとも一部に接着層を備える、請求項1~7の何れかに記載の太陽電池モジュール。
- 前記機能層が電解質層であり、前記太陽電池モジュールが色素増感型太陽電池モジュールである、請求項1~8の何れかに記載の太陽電池モジュール。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17848494.5A EP3511965B1 (en) | 2016-09-06 | 2017-08-04 | Solar battery module |
| KR1020197004094A KR20190040964A (ko) | 2016-09-06 | 2017-08-04 | 태양 전지 모듈 |
| US16/326,554 US10923609B2 (en) | 2016-09-06 | 2017-08-04 | Solar cell module |
| CN201780049854.0A CN109564823B (zh) | 2016-09-06 | 2017-08-04 | 太阳能电池模块 |
| JP2018538308A JP6958559B2 (ja) | 2016-09-06 | 2017-08-04 | 太陽電池モジュール |
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| JP2016173933 | 2016-09-06 |
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| PCT/JP2017/028475 Ceased WO2018047550A1 (ja) | 2016-09-06 | 2017-08-04 | 太陽電池モジュール |
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|---|---|
| US (1) | US10923609B2 (ja) |
| EP (1) | EP3511965B1 (ja) |
| JP (1) | JP6958559B2 (ja) |
| KR (1) | KR20190040964A (ja) |
| CN (1) | CN109564823B (ja) |
| TW (1) | TW201830766A (ja) |
| WO (1) | WO2018047550A1 (ja) |
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| JP2020150223A (ja) * | 2019-03-15 | 2020-09-17 | 積水化学工業株式会社 | 電気モジュール及び電気モジュールの製造方法 |
| WO2021024662A1 (ja) * | 2019-08-02 | 2021-02-11 | 日本ゼオン株式会社 | 光電変換装置 |
| JP2022032849A (ja) * | 2020-08-14 | 2022-02-25 | 日本ゼオン株式会社 | 光電変換素子及び光電変換素子モジュール |
| JP2022073320A (ja) * | 2020-10-30 | 2022-05-17 | 日本ゼオン株式会社 | 硬化性接着剤組成物、光電変換素子および光電変換素子モジュール |
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| US20220336686A1 (en) * | 2021-04-14 | 2022-10-20 | GAF Energy LLC | Photovoltaic module with textured superstrate providing shingle-mimicking appearance |
| TWI860060B (zh) * | 2023-08-25 | 2024-10-21 | 國家原子能科技研究院 | 軟性有機太陽能電池模組的封裝方法及連接該模組的方法 |
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| JP7107788B2 (ja) | 2018-09-03 | 2022-07-27 | 積水化学工業株式会社 | 電気モジュールおよび電気モジュールの製造方法 |
| JP2020150223A (ja) * | 2019-03-15 | 2020-09-17 | 積水化学工業株式会社 | 電気モジュール及び電気モジュールの製造方法 |
| WO2021024662A1 (ja) * | 2019-08-02 | 2021-02-11 | 日本ゼオン株式会社 | 光電変換装置 |
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| JP2022032849A (ja) * | 2020-08-14 | 2022-02-25 | 日本ゼオン株式会社 | 光電変換素子及び光電変換素子モジュール |
| JP7600560B2 (ja) | 2020-08-14 | 2024-12-17 | 日本ゼオン株式会社 | 光電変換素子及び光電変換素子モジュール |
| JP2022073320A (ja) * | 2020-10-30 | 2022-05-17 | 日本ゼオン株式会社 | 硬化性接着剤組成物、光電変換素子および光電変換素子モジュール |
| JP7581774B2 (ja) | 2020-10-30 | 2024-11-13 | 日本ゼオン株式会社 | 硬化性接着剤組成物、光電変換素子および光電変換素子モジュール |
Also Published As
| Publication number | Publication date |
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| EP3511965A4 (en) | 2020-05-06 |
| JPWO2018047550A1 (ja) | 2019-06-24 |
| EP3511965B1 (en) | 2021-09-22 |
| TW201830766A (zh) | 2018-08-16 |
| CN109564823B (zh) | 2021-12-21 |
| EP3511965A1 (en) | 2019-07-17 |
| US20190214512A1 (en) | 2019-07-11 |
| CN109564823A (zh) | 2019-04-02 |
| US10923609B2 (en) | 2021-02-16 |
| KR20190040964A (ko) | 2019-04-19 |
| JP6958559B2 (ja) | 2021-11-02 |
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