WO2016152393A1 - フィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法 - Google Patents
フィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法 Download PDFInfo
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- WO2016152393A1 WO2016152393A1 PCT/JP2016/056033 JP2016056033W WO2016152393A1 WO 2016152393 A1 WO2016152393 A1 WO 2016152393A1 JP 2016056033 W JP2016056033 W JP 2016056033W WO 2016152393 A1 WO2016152393 A1 WO 2016152393A1
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- spacer
- counter electrode
- substrate
- electronic device
- transparent
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Images
Classifications
-
- 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
- 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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
-
- 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
-
- 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
- the present invention relates to an electronic device using a film substrate, a dye-sensitized solar cell, and an electronic device manufacturing method.
- a transparent substrate on which a transparent electrode is formed a counter electrode substrate on which a counter electrode is formed, and a porous substrate formed on the transparent electrode.
- a semiconductor layer formed by supporting a sensitizing dye on a high-quality semiconductor material, a liquid or quasi-liquid electrolyte provided between the semiconductor layer and the counter electrode, and sealing the electrolyte with the transparent substrate A structure including a sealing material for fixing the counter electrode substrate is known.
- Patent Document 1 is a configuration in which a spacer portion is provided at a portion other than the outer peripheral sealing portion, and the transparent substrate and the counter electrode substrate are bonded by the spacer portion, and the adhesion between a pair of substrates is increased by adding such a bonding portion. This improves the durability and has the effect of suppressing the separation of the pair of substrates even when the dye-sensitized solar cell is deformed.
- Patent Document 2 discloses a dye-sensitized solar cell that is provided with a spacer portion between a transparent substrate and a counter electrode substrate at a central portion between sealing materials, and is subjected to sputter deposition on the substrate by thermal expansion / contraction. Even when the warp is warped, the spacer portion at the center portion prevents the distance between the substrates at the center portion from being shortened, and suppresses a decrease in power generation efficiency.
- an electronic device that employs a transparent film having flexibility as a transparent substrate or a counter electrode substrate, it is laminated by passing between heating rolls, so that the portion where the sealing material is disposed and the electrolyte where the sealing material is not disposed There is a possibility that the strength against the pressing force of the roll is different from the portion. For this reason, in the region between the sealing materials, the outside of the film substrate in the thickness direction (the direction in which the transparent substrate and the counter electrode substrate face each other) contracts and the inside extends, and deformation occurs throughout the electronic device. . That is, the gap between the two film substrates is the smallest in the vicinity of the center of the film substrate, and the gap becomes larger toward the edge.
- the thickness of the electrolyte provided between both substrates varies so as to be greatly different between the vicinity of the center of the substrate and the vicinity of the edge. Therefore, when the electronic device configured is a dye-sensitized solar cell, There is a possibility that the power generation efficiency is lowered. Further, when the deformation as described above occurs, the gap between the film substrates becomes non-uniform, and when the film substrate is viewed, the electrolyte 3 looks like a pattern (symbol M in FIG. 16) as shown in FIG. As a result, design properties such as aesthetics are lowered, and there is room for improvement in that respect.
- Patent Documents 1 and 2 have a structure in which a spacer portion is provided. In the region between the spacer portions or between the spacer portion and the sealing material, an electrolyte is disposed between the pair of substrates. In this part, the film substrate is deformed as described above, and there are the same problems as described above.
- the present invention has been made in view of the above-described problems, and is a film base material that can suppress a deterioration in design by suppressing deformation during lamination and maintaining a constant interval between film base materials.
- An object of the present invention is to provide an electronic device, a dye-sensitized solar cell, and a method for manufacturing the electronic device.
- An electronic device using a film substrate according to an embodiment of the present invention is a porous substrate formed on a transparent substrate on which a transparent electrode is formed, a counter electrode substrate on which a counter electrode is formed, and the transparent electrode.
- a spacer is interposed between the semiconductor layer and the counter electrode substrate in the electrolyte between the sealing materials, a transparent film having flexibility is used for the transparent substrate and the counter electrode substrate.
- the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- the spacer since the spacer is sandwiched between the semiconductor layer and the counter electrode substrate, the spacer does not function as a spacer so that the spacer is pushed and moved in one direction together with the pressing of the heating roll, The position of the spacer is held between the semiconductor layer and the counter electrode substrate.
- the transparent substrate and the counter electrode substrate are not brought into contact with each other, and the change in the thickness of the electrolyte can be suppressed to be small, and the decrease in power generation efficiency can be suppressed.
- the thickness of the electrolyte is constant, the electrolyte having a non-uniform thickness does not look like a pattern through the transparent film, and the design can be prevented from being deteriorated.
- the spacer is provided between the semiconductor layer and the counter electrode substrate, it is possible to scatter incident light and return it to the semiconductor electrode again, thereby improving the power generation efficiency. it can.
- the spacer is made of a material that is thermally expanded by heating, and between the transparent substrate and the counter electrode substrate in a thermally expanded state. It may be clamped and fixed.
- the spacer is thermally expanded by heating during laminating that is passed between heating rolls during the manufacture of the electronic device, and the expanded spacer is interposed between the transparent substrate and the counter electrode substrate. Therefore, the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- the spacer has a property of thermally expanding at a heating temperature at the time of lamination in which the electronic device is passed between heating rolls. Also good.
- the spacer preferably has a characteristic that its volume is thermally expanded by 3% or more in a range lower by 0 ° C. to 20 ° C. than the surface temperature of the heating roll. More preferably, it is 5% or more, more preferably 10% or more. Further, it preferably has a characteristic that the volume expands by 25% or less in the range of 0 ° C. to 20 ° C. More preferably, it is 20% or less, and further preferably 15% or less.
- the spacer is surely thermally expanded when the heating temperature at the time of lamination is reached, and the expanded spacer is interposed between the transparent substrate and the counter electrode substrate.
- the spacer is fixed to at least one of the semiconductor layer and the counter electrode substrate, and the transparent electrode and the counter electrode May be formed in a protruding shape that protrudes inward in the opposing direction.
- the heating roll at the time of manufacturing the electronic device Even if the pressing force of the heating roll is applied during lamination, the transparent substrate made of the film substrate and the counter electrode substrate are not deformed in the direction of approaching each other, and the separation between the two can be kept constant. it can.
- the spacer is made of a material that melts by heating, and the adjacent spacers in a state where the surface is melted, or the spacer and the spacer The substrates may be bonded together.
- the surface of the spacer is melted or softened by heating during laminating that is passed between heating rolls in the manufacture of the electronic device, and the adjacent spacers that have been melted or softened or the spacer and the substrate are bonded to each other. Since the spacer is interposed between the transparent substrate and the counter electrode substrate, the distance between the transparent substrate and the counter electrode substrate can be kept constant.
- the spacer is melted or softened at the heating temperature at the time of lamination in which the electronic device is passed between heating rolls, and the adhesive property is increased. You may make it have the characteristic which expresses.
- the surface of the spacer is surely melted or softened when the heating temperature at the time of lamination is reached, and the melted spacer is interposed between the transparent substrate and the counter electrode substrate.
- the material that melts or softens and exhibits adhesiveness include thermoplastic resins and resin compositions containing thermoplastic resins. Examples thereof include a porous body made of the resin composition containing bubbles and a resin composition made of the resin containing a foaming agent.
- the spacer has a sharp projecting portion formed on an outer periphery, the adjacent spacers are combined, or the spacer, At least one of the pair of transparent electrodes and the counter electrode may be coupled.
- the spacer is coupled to at least one of the pair of transparent electrodes and the counter electrode by engaging the sharp projecting portion of the spacer.
- the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- the spacer may have a property of expanding due to heat or light of UV irradiation.
- the spacer is expanded by the heat or light of UV irradiation during the manufacture of the electronic device, and the expanded spacer is interposed between the transparent substrate and the counter electrode substrate.
- the distance between the counter electrode substrate and the counter electrode substrate can be kept constant.
- the spacer may have a property that the surface is melted or softened by heat or light of UV irradiation.
- the surface of the spacer is melted or softened by the heat or light of UV irradiation at the time of manufacturing the electronic device, and the melted or softened adjacent spacers, or the spacer and the substrate are combined, and the spacer is a transparent substrate. Since it is interposed between the transparent substrate and the counter electrode substrate, the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- the spacer may be made of a gel particle material having a property of absorbing and swelling the electrolyte.
- the gel particles are foamed (expanded) by absorbing the electrolyte during the manufacture of the electronic device, and the expanded gel particles are interposed between the transparent substrate and the counter electrode substrate. Therefore, the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- Another aspect of the present invention is a dye-sensitized solar cell constituting the electronic device according to the above (1) to (10).
- a sensitizing dye is supported on a transparent substrate on which a transparent electrode is formed, a counter electrode substrate on which a counter electrode is formed, and a porous semiconductor material formed on the transparent electrode.
- a liquid layer or a quasi-liquid electrolyte provided between the semiconductor layer and the counter electrode, and a sealing material for sealing the electrolyte and fixing the transparent substrate and the counter electrode substrate
- a current collector wiring disposed in an end portion of the semiconductor layer and extending in a direction parallel to and intersecting with the extending direction of the sealing material, and dye sensitization constituting an electronic device using a film substrate
- the transparent substrate and the counter electrode substrate are each formed of a flexible transparent film, and a spacer is sandwiched between the semiconductor layer and the counter electrode substrate in the electrolyte, and the current collector At least part of the wiring , Toward the counter electrode substrate toward the entire length of the current collector wire protrudes from the semiconductor layer, a dye-sensitized solar cell.
- Another aspect of the present invention is the method for manufacturing an electronic device according to any one of the above (1) to (10), wherein the semiconductor layer and the counter electrode substrate in the electrolyte between the sealing materials And a step of laminating by passing the electronic device between heating rolls, and during the lamination, the spacer is disposed between the semiconductor layer and the counter electrode substrate, respectively.
- the electronic device using the film substrate, the dye-sensitized solar cell, and the manufacturing method of the electronic device according to each aspect of the present invention deformation during lamination is suppressed and the distance between the film substrates is kept constant. Thereby, the fall of the designability can be suppressed.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a dye-sensitized solar cell according to a first embodiment of the present invention.
- FIG. 2 is a plan view showing a part of the dye-sensitized solar cell, taken along the line AA in FIG.
- FIG. 3 is a partially separated sectional view showing a schematic configuration before lamination of the dye-sensitized solar cell shown in FIG.
- FIG. 4 is a cross-sectional view showing a state before the spacer is thermally expanded in the laminate.
- FIG. 5 is a partially separated sectional view showing a schematic configuration before lamination of the dye-sensitized solar cell according to the second embodiment.
- FIG. 6 is a cross-sectional view showing a schematic configuration after lamination of the dye-sensitized solar cell shown in FIG.
- FIG. 7 is a partially separated sectional view showing a schematic configuration before lamination of the dye-sensitized solar cell according to the third embodiment.
- FIG. 8 is a cross-sectional view showing a schematic configuration after lamination of the dye-sensitized solar cell shown in FIG.
- FIG. 9 is a cross-sectional view showing a schematic configuration after lamination of the dye-sensitized solar cell according to the fourth embodiment.
- FIG. 10A is a side view showing a process during lamination of the dye-sensitized solar cell according to the fifth embodiment.
- FIG. 10A is a side view showing a process during lamination of the dye-sensitized solar cell according to the fifth embodiment.
- FIG. 10B is a side view showing a process of laminating another dye-sensitized solar cell according to the fifth embodiment.
- FIG. 11A is a cross-sectional view showing a state before lamination of the dye-sensitized solar cell according to the fifth embodiment.
- FIG. 11B is a cross-sectional view showing a state when the dye-sensitized solar cell according to the fifth embodiment is laminated, and shows a state when UV irradiation is performed.
- FIG. 11C is a cross-sectional view showing a state after lamination of the dye-sensitized solar cell according to the fifth embodiment, and is a view showing a state in which the spacer is expanded by UV irradiation.
- FIG. 11A is a cross-sectional view showing a state before lamination of the dye-sensitized solar cell according to the fifth embodiment.
- FIG. 11B is a cross-sectional view showing a state when the dye-sensitized solar cell according
- FIG. 12 is a cross-sectional view showing a state after lamination of the dye-sensitized solar cell according to the sixth embodiment, and is a view showing a state in which a spacer is melted by UV irradiation.
- FIG. 13 is a plan view showing a state after lamination of the dye-sensitized solar cell according to the seventh embodiment.
- FIG. 14 is a sectional view showing a state after lamination of the dye-sensitized solar cell according to the seventh embodiment, and is a sectional view taken along line BB shown in FIG.
- FIG. 15A is a cross-sectional view showing a state before lamination of the dye-sensitized solar cell according to the eighth embodiment.
- FIG. 15B is a cross-sectional view showing a state after lamination of the dye-sensitized solar cell according to the eighth embodiment.
- FIG. 16 is a top view after conventional lamination.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a dye-sensitized solar cell 10.
- the dye-sensitized solar cell 10 includes a semiconductor electrode 1, a counter electrode 2, an electrolyte 3, a conductive material 4 with a sealing function, and a spacer 5.
- the dye-sensitized solar cell 10 includes a transparent substrate 11 on which a transparent conductive film 12 (transparent electrode) is formed, a counter electrode substrate 21 on which a counter conductive film 22 (counter electrode) is formed, and the transparent conductive film 12.
- a semiconductor layer 13 formed by supporting a known sensitizing dye on a porous semiconductor material, a liquid or quasi-liquid electrolyte 3 provided between the semiconductor layer 13 and the counter conductive film 22, and an electrolyte.
- a conductive material 4 with a sealing function having a sealing material 41 for sealing 3 and fixing the transparent substrate 11 and the counter electrode substrate 21 together.
- the semiconductor electrode 1 includes the transparent substrate 11, a transparent conductive film 12 stacked on the transparent substrate 11, and a semiconductor layer 13 stacked on the transparent conductive film 12.
- a known sensitizing dye is adsorbed to the semiconductor layer 13 on the surface including the porous interior with which the electrolyte 3 contacts.
- the counter electrode 2 includes a counter electrode substrate 21, a counter conductive film 22 stacked on the counter electrode substrate 21, and a catalyst layer (not shown) stacked on the counter conductive film 22.
- the conducting material 4 with a sealing function includes a sealing material 41 and a conducting material 42.
- the sealing material 41 forms a power generation unit (cell) composed of the semiconductor electrode 1, the counter electrode 2, and the electrolyte 3 so as to surround the semiconductor layer 13, and seals by dividing (separating) adjacent cells. It is provided for.
- a gap is formed between the semiconductor electrode 1 and the counter electrode 2 by the conductive material 4 with a sealing function, and the electrolyte 3 is sealed in the gap.
- the conducting material 42 of the conducting material 4 with the sealing function is arranged on the opposite side of the electrolyte 3 with the sealing material 41 interposed therebetween, and is directly on the transparent conductive film 12 and the opposing conductive film 22 constituting the semiconductor electrode 1 and the counter electrode 2.
- the sealing material 41 is provided in close contact with the conductive material 42 and in close contact with the transparent conductive film 12 and the counter conductive film 22.
- the sealing material 41 is illustrated so as to be in close contact with the conductive material 42, but may be separated.
- the conductive material 42 may have both functions of conduction and adhesion, like a double-sided adhesive type copper tape.
- a plurality of cuts are provided at predetermined positions of the transparent conductive film 12 and the counter conductive film 22 by a laser irradiation cutter or the like, and electrodes between adjacent cells are provided.
- (Semiconductor electrode 1 and counter electrode 2) are divided into a plurality of sections.
- the transparent conductive film 22 constituting the counter electrode 2 of the first cell and the transparent conductive film 12 constituting the semiconductor electrode 1 of the second cell adjacent to the first cell are conductive materials. 42 is electrically connected. As a result, the first cell and the second cell described above are connected in series.
- the spacer 5 is interposed between the semiconductor layer 13 and the counter electrode substrate 21 (catalyst layer) and fixed in the electrolyte 3 between the sealing materials 41 and 41, and is disposed at irregular positions.
- the spacer 5 is spherical, but is not limited to being spherical.
- the spacer 5 is made of a material that is thermally expanded by heating, is sandwiched and fixed between the transparent substrate 11 and the counter electrode substrate 21 in a thermally expanded state, and has a shape smaller than that after thermal expansion before the thermal expansion before lamination. It is.
- the spacer 5 examples include expanded graphite, polystyrene beads in which a foaming agent is incorporated (foamed and expanded by heat), and the like, and a heating temperature at the time of lamination that allows the dye-sensitized solar cell 1 to pass between heating rolls. It preferably has the property of thermal expansion at Further, the spacer 5 may be disposed in the region of the electrolyte 3. By arranging the spacer 5 in the region of the electrolyte 3, it becomes easier to maintain the interval between the transparent substrate 11 and the counter electrode substrate 21.
- the material of the spacer is preferably a material that is not easily deteriorated by the electrolyte. For example, materials such as silicon resin and fluorine resin can be exemplified.
- the transparent substrate 11 and the counter electrode substrate 21 are each formed from a flexible transparent film.
- the material of the transparent substrate 11 and the counter electrode substrate 21 made of a transparent film substrate constituting the semiconductor electrode 1 and the counter electrode 2 include insulators such as glass and resin.
- this resin include poly (meth) acrylic acid ester, polycarbonate, polyester, polyimide, polystyrene, polyvinyl chloride, and polyamide.
- the substrate is more preferably glass, PET film or PEN film.
- the thickness is 0.5 mm or less because it has flexibility. A more preferable thickness is 0.3 mm or less.
- the kind of the transparent conductive film 12 and the counter conductive film 22 is not particularly limited, and a conductive film used for a known dye-sensitized solar cell is applicable, and examples thereof include a thin film made of a metal oxide.
- a metal oxide include those known by abbreviations such as ITO, FTO, ATO, IZO, and GZO.
- the semiconductor layer 13 is made of a material capable of receiving electrons from the adsorbed sensitizing dye, and is usually preferably porous.
- the material which comprises the semiconductor layer 13 is not specifically limited, The material of a well-known semiconductor layer is applicable, For example, metal oxide semiconductors, such as a titanium oxide, a zinc oxide, a tin oxide, are mentioned.
- the sensitizing dye supported on the semiconductor layer 13 is not particularly limited, and examples thereof include known dyes such as organic dyes and metal complex dyes.
- organic dyes include coumarin, polyene, cyanine, hemicyanine, and thiophene.
- metal complex dye for example, a ruthenium complex is preferably used.
- the material constituting the catalyst layer is not particularly limited, and known materials can be applied, and examples thereof include carbons such as platinum and carbon nanotubes, and conductive polymers such as PEDOT / PSS.
- the type of the electrolyte 3 is not particularly limited, and an electrolyte used in a known dye-sensitized solar cell can be applied.
- an electrolytic solution in which iodine and lithium iodide are dissolved in an organic solvent can be used as the redox pair (electrolyte).
- the conducting material 42 constituting the conducting material 4 with the sealing function is not particularly limited as long as it is a member that can electrically conduct the electrodes formed on the two opposing base materials 11 and 21.
- the conductive material 42 for example, at least one selected from a conductive wire, a conductive tube, a conductive foil, a conductive plate and a conductive mesh, and a conductive paste is used.
- the conductive paste is a conductive material having a relatively low rigidity and a soft form.
- the conductive paste may have a form in which a solid conductive material is dispersed in a viscous dispersion medium such as an organic solvent or a binder resin.
- the conducting material 42 may have both functions of conduction and adhesion like a double-sided adhesive type copper tape.
- Examples of the conductive material 42 include metals such as gold, silver, copper, chromium, titanium, platinum, nickel, tungsten, iron, and aluminum, or alloys of two or more of these metals. Not. Examples of the material include resin compositions such as polyurethane and polytetrafluoroethylene (PTFE) in which conductive fine particles (for example, fine particles of metal or alloy, fine particles of carbon black, etc.) are dispersed.
- metals such as gold, silver, copper, chromium, titanium, platinum, nickel, tungsten, iron, and aluminum, or alloys of two or more of these metals.
- the material include resin compositions such as polyurethane and polytetrafluoroethylene (PTFE) in which conductive fine particles (for example, fine particles of metal or alloy, fine particles of carbon black, etc.) are dispersed.
- PTFE polytetrafluoroethylene
- the sealing material 41 constituting the conductive material with a sealing function 4 is a dye-sensitized solar cell module formed by adhering two opposing base materials 11 and 21 and formed between the two base materials 11 and 21. Any non-conductive member that can be sealed is not particularly limited.
- a hot melt adhesive thermoplastic resin
- thermosetting resin thermosetting resin
- ultraviolet curable resin a resin including an ultraviolet curable resin and a thermosetting resin
- resin material that has fluidity and is solidified by an appropriate treatment examples of the hot melt adhesive include polyolefin resin, polyester resin, polyamide resin, and the like.
- the thermosetting resin include an epoxy resin and a benzoxazone resin.
- the ultraviolet curable resin include those containing a photopolymerizable monomer such as acrylic acid ester and methacrylic acid ester.
- action of the dye-sensitized solar cell 10 using the film base mentioned above are demonstrated in detail using drawing.
- a manufacturing method of the dye-sensitized solar cell 10 using the film base material having the above-described configuration as shown in FIG. 3, in the electrolyte 3 between the sealing materials 41, 41, the semiconductor layer 13 and the counter electrode substrate 21.
- the spacer 5 and the electrolyte 3 before thermal expansion are disposed on the semiconductor layer 13.
- the dye-sensitized solar cell 10 in which the semiconductor electrode 1 and the counter electrode 2 are superposed is passed between heating rolls (not shown) and laminated.
- the spacer 5 may be dispersed in the electrolyte 3 in advance.
- the thermally expanded spacer 5 is interposed and fixed in the electrolyte 3 between the sealing materials 41 and 41 between the semiconductor layer 13 and the counter electrode substrate 21. Therefore, when the transparent substrate 11 and the counter electrode substrate 21 are laminated by passing the dye-sensitized solar cell 10 using a transparent film having flexibility between heating rolls (not shown), the transparent substrate 11 and the counter electrode substrate 21. Can be kept constant. That is, as shown in FIG. 4, the spacer 5 is thermally expanded by the heating during the lamination that is passed between the heating rolls during the manufacture of the electronic device, and the expanded spacer 5 is formed of the transparent substrate 11 and the counter electrode substrate as shown in FIG. 1. Therefore, the distance between the transparent substrate 11 and the counter electrode substrate 21 can be kept constant.
- the spacers 5 are sandwiched and fixed between the semiconductor layer 13 and the counter electrode substrate 21 during lamination, the spacers 5 are pushed out in one direction and moved together with the pressing of the heating roll. The position of the spacer 5 is held between the semiconductor layer 13 and the counter electrode substrate 21 without functioning.
- the transparent substrate 11 and the counter electrode substrate 21 are not brought into contact with each other, and the change in the thickness of the electrolyte 3 can be suppressed to a low level, resulting in a decrease in power generation efficiency. Can be suppressed.
- the thickness of the electrolyte 3 is constant, the electrolyte having a non-uniform thickness does not look like a pattern through the transparent film, and the design can be prevented from being deteriorated.
- the spacer 5 is provided between the semiconductor layer 13 and the counter electrode substrate 21, it is possible to scatter incident light and return it to the semiconductor electrode again. Improvements can be made.
- the spacer 5 ⁇ / b> A according to the second embodiment is fixed to the counter electrode substrate 21 and protrudes inward in the direction in which the transparent substrate 11 and the counter electrode substrate 21 face each other. It is formed in a protruding shape.
- the protruding spacers 5A are suspended in advance in a column shape with respect to the inner surface 21a of the counter electrode substrate 21 before lamination, and a plurality of the spacers 5A are provided intermittently (discontinuously).
- the height dimension h of the spacer 5A coincides with the distance between the laminated semiconductor layer 13 and the counter electrode substrate 21 (opposing conductive film 22).
- the cross-sectional shape of the spacer 5A is not limited to a circle or a square. The cross-sectional shape may be the same or may change along the protruding direction, but the protruding end in contact with the semiconductor layer 13 is preferably a plane parallel to the semiconductor layer 13.
- the protruding spacer 5A is fixed to the counter electrode substrate 21, but a plurality of protruding spacers 5A may be provided near the semiconductor layer 13. The point is that the spacer 5A may be fixed to at least one of the semiconductor layer 13 and the counter electrode substrate 21.
- the protruding spacer 5A fixed to the counter electrode substrate 21 is disposed between the transparent substrate 11 and the counter electrode substrate 21, the dye-sensitized solar cell 10 is manufactured. Even when a pressing force of the heating roll is applied during laminating between the heating rolls at the time, the transparent substrate 11 made of a film substrate and the counter electrode substrate 21 are not deformed in the direction in which they are close to each other. Can be kept constant.
- the dye-sensitized solar cell 10 according to the third embodiment is made of a material in which the spacer 5B is melted by heating, and the adjacent spacers 5B and 5B are in a state where the surfaces are melted. It is a combined configuration.
- the spacer 5B has a characteristic that the surface is melted or softened at a heating temperature at the time of lamination in which the dye-sensitized solar cell 10 is passed between heating rolls.
- the spacer 5B of the present embodiment is a member that does not thermally expand as in the first embodiment described above, the size is approximately the same before and after lamination, and the transparent substrate 11 and the counter electrode substrate 21 after lamination are the same.
- the dimension is set so as to be interposed and fixed between the two.
- the spacer 5B may be dispersed in the electrolyte 3.
- Examples of such a spacer 5B include a material in which thermoplastic resin fine particles (insulating material such as rubber particles or thermoplastic elastomer particles) are melted or softened by heat and the spacers 5B and 5B are bonded to each other. Further, a material in which rubber particles are crushed by pressure and adhered to each other, that is, a material in which polymer fine particles having reactive functional groups on the surface of the spacer 5B are polymerized by heat, and the like are also included.
- thermoplastic resin fine particles insulating material such as rubber particles or thermoplastic elastomer particles
- the surface of the spacer 5B is melted or softened by heating at the time of lamination that is passed between heating rolls in the production of the dye-sensitized solar cell 10, and the adjacent spacer 5B that has been melted or softened, Since 5B couple
- substrate 21 can be kept constant.
- the spacer 5B has a characteristic that the surface melts at the heating temperature at the time of lamination that allows the dye-sensitized solar cell 10 to pass between the heating rolls, so that the heating temperature at the time of lamination has been reached. Sometimes the surface of the spacer 5B can be reliably melted or softened.
- the spacer 5C is made of a material that is melted or softened by heating, and the spacer 5C and the counter electrode substrate 21 are joined together in a state where the surface is melted or softened.
- the spacer 5C has a characteristic that the surface is melted or softened at a heating temperature at the time of lamination in which the dye-sensitized solar cell 10 is passed between heating rolls.
- the spacer 5C of the present embodiment can be made of the same material as that of the second embodiment described above, and is approximately the same size before and after lamination.
- the laminated transparent substrate 11 and counter electrode substrate 21 The dimension is set so as to be interposed and fixed in between.
- the surface of the spacer 5C is melted or softened by heating at the time of lamination that is passed between heating rolls in the production of the dye-sensitized solar cell 10, and the fused or softened spacer 5C and the counter electrode substrate 21 are coupled to each other and the spacer 5C is interposed between the transparent substrate 11 and the counter electrode substrate 21, so that the separation between the transparent substrate 11 and the counter electrode substrate 21 can be kept constant.
- the spacer 5C has a characteristic that the surface is melted or softened at the heating temperature at the time of lamination in which the dye-sensitized solar cell 10 is passed between the heating rolls. When it reaches, the surface of the spacer 5C can be reliably melted.
- the fifth embodiment is a method for manufacturing a dye-sensitized solar cell using the UV irradiation apparatus 7 shown in FIGS. 10A and 10B. As shown in FIG. 11A, FIG. 11B, and FIG.
- the spacer 5D is made of a thermosetting or photo-curing resin material having a characteristic of foaming (expanding) by heat or light (ultraviolet rays) due to UV irradiation, Like the first embodiment described above, the substrate is sandwiched and fixed between the transparent substrate 11 and the counter electrode substrate 21 in an expanded state.
- the plurality of spacers 5D have a shape smaller than that after expansion in a state before expansion before UV irradiation in a UV irradiation process included in a part of the manufacturing process of the dye-sensitized solar cell 10.
- a plurality of spacers 5 ⁇ / b> D are arranged at irregular positions in the electrolyte 3 between the sealing materials 41 and 41.
- the spacer 5D has a spherical shape.
- the spacer 5D is not limited to a spherical shape, and can be arranged in any shape.
- the wavelength and intensity of the ultraviolet rays irradiated to the spacer 5D by the UV irradiation device 7 are appropriately set according to conditions such as the resin expansion coefficient and the resin type of the spacer 5D used. Further, the number of UV irradiation devices 7 arranged in the present embodiment is two or three in the transport direction, but is not limited to this number.
- the above-described UV irradiation in the fifth embodiment is employed in the bonding process of the transparent substrate 11 and the counter electrode substrate 21.
- the UV irradiation device 7 is provided on the downstream side in the transport direction of the first press rolls 6A, 6A. Further, a pair of first press rolls 6 ⁇ / b> B and 6 ⁇ / b> B are provided near the downstream side of the UV irradiation device 7.
- the UV irradiation device 7 is composed of a commercially available ultraviolet light source or an ultraviolet ray emitting part guided by an optical fiber or the like from the ultraviolet light source installed at a remote location.
- the amount of light of ultraviolet rays in the irradiation region of ultraviolet rays emitted from the UV irradiation device 7 is not particularly limited as long as it reaches the amount of light necessary for the expansion of the spacer 5D, for example.
- a method for manufacturing the dye-sensitized solar cell 10 using such a spacer 5D made of UV resin will be described.
- an ultraviolet curable resin is used for the sealing material 41, and in the electrolyte 3 between the sealing materials 41 and 41, the UV light is irradiated on the semiconductor layer 13 between the transparent substrate 11 and the counter electrode substrate 21 before UV irradiation.
- Spacer 5D and electrolyte 3 are arranged.
- the sealing material 41 is cured by irradiating the dye-sensitized solar cell 10 in which the semiconductor electrode 1 and the counter electrode 2 are overlapped by the first press rolls 6 ⁇ / b> A and 6 ⁇ / b> A with the UV irradiation device 7 described above.
- Laminate The spacer 5D may be dispersed in the electrolyte 3 in advance.
- the transparent substrate 11 and the counter electrode substrate 21 are not in contact with each other, and the change in the thickness of the electrolyte 3 is suppressed to be small. It is possible to suppress the decrease in power generation efficiency. And like embodiment mentioned above, since the thickness of the electrolyte 3 becomes fixed, an electrolyte with non-uniform thickness does not look like a pattern through a transparent film, and the fall of designability is prevented. Can do.
- the second press rolls 6B and 6B are allowed to pass further after UV irradiation, thereby providing a function of removing air bubbles between the substrates that cannot be removed by the first press rolls 6A and 6A. Yes. Therefore, in this case, since the second press rolls 6B and 6B have the same or narrow gap as the first press rolls 6A and 6A, the spacer 5D is located upstream of the second press rolls 6B and 6B (the first press roll 6A and the second press roll 6B) needs to expand to a predetermined size.
- the dye-sensitized solar cell 10 is a thermosetting or photocurable resin having a property that the spacer 5E is melted by heat or light (ultraviolet rays) due to UV irradiation. It is made of a material or particles, and has a configuration in which the adjacent spacers 5E and 5E are joined in a state where the surface is melted.
- the spacer 5E is set to a size that is interposed between the transparent substrate 11 after UV irradiation and the counter electrode substrate 21 in a fixed state.
- the spacer 5E may be dispersed in the electrolyte 3.
- the wavelength of the ultraviolet rays irradiated to the spacer 5E by the UV irradiation device 7 is appropriately set according to conditions such as the type of resin of the spacer 5E used.
- the number of UV irradiation devices 7 arranged is the same as in the fifth embodiment described above.
- the surface of the spacer 5E is melted or softened by heat or light due to UV irradiation at the time of manufacturing the dye-sensitized solar cell 10, and the melted or softened adjacent spacers 5E and 5E are bonded to each other.
- the spacer 5E is interposed between the transparent substrate 11 and the counter electrode substrate 21, the separation between the transparent substrate 11 and the counter electrode substrate 21 can be kept constant.
- the dye-sensitized solar cell 10 according to the seventh embodiment shown in FIG. 13 is provided on the transparent substrate 11 on which the transparent conductive film 12 is formed, and at the end of the semiconductor layer 13.
- a protective member 43 that covers the current collector wiring 44 that is disposed and extends in a direction that is parallel to and orthogonal to (intersects) the extending direction of the sealing material is provided, and a protruding portion that protrudes toward the counter electrode 2 from the protective material 43 43a is provided.
- the protrusion 43 a protrudes from a part of the width direction of the protective material 43 (central portion) and is formed along the extending direction of the current collector wiring 44.
- the holding member 43 including the protrusion 43 a is a part of the current collector wiring 44.
- the thickness of the semiconductor layer 13 and the thickness of the protective material 43 including the current collecting wiring 44 are substantially the same, and the protrusion 43 a protrudes closer to the counter substrate 21 than the semiconductor layer 13.
- the spacer 5 When the spacer 5 is laminated by passing the dye-sensitized solar cell 10 in which the semiconductor electrode 1 and the counter electrode 2 are superposed between the heating rolls 6, the spacers 5 are kept apart from each other. A dimension that does not bend is selected.
- simple particles that are not expanded by heat, light (UV) or the like in the process of lamination are used.
- the spacer 5 is preferably a particle having a constant particle size or a particle that is crushed by pressurization (described in an eighth embodiment described later).
- inorganic particles or organic-inorganic composite particles are preferable. And it is preferable to use the spacer 5 in the state mixed with the electrolyte 3.
- the current collection wiring 44 and the protective material 43 can be produced by well-known methods, such as screen printing, transfer, and application
- the spacer 5 is not only pressed together with the pressing of the heating roll 6 during lamination as shown in FIG. It is possible to provide a stopper function for restricting movement by being pushed in the direction, and the position of the spacer 5 can be held between the semiconductor layer 13 and the counter electrode substrate 21.
- the extending direction of the protrusion 43a (the current collector wiring 44) is arranged in an oblique direction intersecting with the extending direction of the sealing material as long as it has a stopper function for restricting the movement of the spacer 5.
- the direction is not necessarily limited to the orthogonal direction.
- the protrusion 43a is not limited to one in which a part (center part) in the width direction of the protective material 43 protrudes, and it is preferable that the protective material 43 protrudes with the full width.
- the height of the current collector wiring 44 itself may be lower or higher than that of the semiconductor layer 13 because the protrusion 43a only needs to protrude closer to the counter electrode substrate 21 than the semiconductor layer 13 as described above. It doesn't matter.
- the protective material 43 and the semiconductor layer 13 are in contact with each other in the present embodiment, a gap may be formed.
- the manufacturing method of the dye-sensitized solar cell 10 according to the eighth embodiment shown in FIGS. 15A and 15B is a method using a spacer 5F made of a resin particle material having flexibility to cause elastic deformation by pressure.
- the diameter D1 (FIG. 15A) of the spacer 5F before elastic deformation is the distance D2 (gap) between the transparent substrate 11 and the counter substrate 21 of the final dye-sensitized solar cell 10 manufactured as shown in FIG. 15B.
- Larger ones are used.
- the dimension of the spacer 5F is 3% or more, more preferably 5% or more, more preferably 10% or more, and 25% or less of the target gap (final gap when the spacer 5F is crushed).
- the size is 20% or less, more preferably 15% or less. Note that if the size is larger than this size range, the area in contact with the upper and lower substrates 11 and 12 will be increased when crushed by elastic deformation, and the power generation efficiency will be reduced. On the other hand, if the size is too smaller than the size range, the function as a gap retention agent is lowered.
- the resin particles of the spacer 5F only need to contain a resin component, and are not limited to particles composed only of organic materials, but may be particles composed of organic-inorganic composite materials.
- resin particles By using resin particles as a base material, flexible particles having excellent elastic deformation characteristics can be obtained.
- what is necessary is just to select the optimal compression elastic modulus of a soft particle according to the base material to be used or the crushing ratio. If the compressive elastic modulus is too large, the particles may be elastically deformed after lamination and become larger than a predetermined gap, resulting in a decrease in efficiency. On the other hand, if the compression elastic modulus is too small, the force for maintaining the gap between the two substrates cannot be obtained, and the substrate is bent.
- the compression elastic modulus of the spacer 5F is, for example, a method of adjusting the blending ratio of the crosslinkable monomer and the noncrosslinkable monomer constituting the flexible particle to change the crosslink density, or a flexible single amount. It can be changed by a known method such as a method of adjusting the blending amount of the body.
- the material of the resin particles of the spacer 5F is most preferably organic particles that have flexibility during pressing and have a small specific gravity. That is, by using organic particles, when mixing with the electrolytic solution, by selecting organic particles having the smallest specific gravity, it is possible to suppress sedimentation as in the case where the specific gravity is large.
- the CV value (coefficient of variation) of the resin particles of the spacer 5F is a particle having a CV value equal to or less than that of the particles put in the sealing material and the conductive material. When this CV value is larger than the surrounding particles, the gap is wider than the design value, resulting in a decrease in aesthetics.
- the CV value is calculated by dividing the standard deviation by the arithmetic average.
- the particles of the spacer 5F are elastically deformed by lamination with a heating roll. That is, when the base material is bent to a predetermined gap or less, the soft particles repel and a restoring force is generated, so that the distance between the transparent substrate 11 and the counter electrode substrate 12 can be kept constant. it can.
- the flexible particles of the spacer 5F are elastically deformed, the flexible particles are sandwiched and hooked by the upper and lower substrates, and the movement before and after the lamination can be suppressed.
- the resin particle of the spacer 5F is previously mixed with electrolyte solution, and it is set as the timing same as filling of electrolyte solution. preferable.
- the spacer 5 is made of a gel particle material having a characteristic of absorbing (water absorption) the electrolyte solution (reference numeral 3) and swelling.
- Examples of the spacer 5 made of gel particles include gel fine particles obtained by dissolving N-isopropylacrylamide as a monomer and a crosslinking agent in warm water and performing radical polymerization.
- a polyfunctional monomer can be used, for example, N, N′-methylenebisacrylamide and the like can be used.
- What is necessary is just to select the optimal thing for the swelling ratio of this gel-like particle
- the adjustment of the swelling ratio and the swelling speed has a functional group that interacts with the solvent used in the method for controlling the addition amount of the crosslinking agent when producing the gel fine particles and adjusting the degree of crosslinking and the electrolyte.
- the volume expands by 3% or more. More preferably, it is 5% or more, more preferably 10% or more. It is preferable that the volume expands by 25% or less. More preferably, it is 20% or less, and further preferably 15% or less.
- Gel particles may be blended in advance in the electrolytic solution, placed on the substrate before applying the electrolytic solution, or distributed to the substrate after applying the electrolytic solution. From the viewpoint of manufacturability, a method of blending in an electrolytic solution and applying it before swelling completely is preferable.
- the spacer 5 and the electrolytic solution are arranged on the semiconductor layer 13 between the transparent substrate 11 and the counter electrode substrate 21. Then, it laminates with respect to the dye-sensitized solar cell 10 which accumulated the semiconductor electrode 1 and the counter electrode 2.
- FIG. At this time, the electrolyte 3 is absorbed (water absorption) by the spacer 5 in the electrolytic solution between the semiconductor layer 13 and the counter electrode substrate 21 in the electrolytic solution, the spacer 5 swells (expands), and the expanded spacer 5 is transparent. Since it is interposed between the substrate 11 and the counter electrode substrate 21, the separation between the transparent substrate 11 and the counter electrode substrate 21 can be kept constant.
- the surfaces of the spacers 5B and 5C are melted or softened by heat so that the spacers or the spacers and the substrates are bonded to each other.
- the spacer a member in which a sharp projecting portion is formed on the outer periphery is used, and adjacent spacers are coupled to each other, or the spacer is coupled to at least one of a pair of transparent electrodes and a counter electrode. It is also possible to do.
- the spacer has a configuration in which the outer peripheral surface of the spacer has a convex shape around it, such as a sea urchin, and is fixed by meshing like a gear or by being stuck into a substrate. It is also possible.
- the adjacent spacers when the pressing force of the heating roll is applied during the lamination that is passed between the heating rolls in the manufacture of an electronic device such as a dye-sensitized solar cell, the adjacent spacers have their respective sharp protrusions.
- the spacers are coupled to each other, or the spacer is coupled to at least one of the pair of transparent electrodes and the counter electrode by the engagement of the sharp projecting portion of the spacer.
- the spacer since the spacer is interposed between the transparent substrate and the counter electrode substrate, the separation between the transparent substrate and the counter electrode substrate can be kept constant.
- a foamed body such as a nonwoven fabric or sponge impregnated with an electrolytic solution may be used as a spacer and provided in a region where the electrolyte 3 is disposed.
- the shape of the spacer is not limited to the spherical shape as in the above-described embodiment, and may be a columnar shape (a prismatic shape, a conical shape, a cylindrical shape) or the like.
- a spacer in the electrolyte between the sealing materials, is sandwiched and fixed between the semiconductor layer and the counter electrode substrate. It is not limited to being fixed to the layer and the counter electrode substrate.
- the spacer may be simply held in contact with the semiconductor layer and the counter electrode substrate.
- the method for manufacturing an electronic device, a dye-sensitized solar cell, and an electronic device using the film base material of the present invention it is possible to suppress deformation during lamination and to maintain a constant spacing between the film base materials. Can be suppressed.
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Abstract
Description
本願は、2015年3月23日に、日本国に出願された特願2015-060227号に基づき優先権を主張し、その内容をここに援用する。
特許文献1は、外周の封止部以外においてスペーサ部を設け、このスペーサ部によって透明基板と対極基板と接着する構成であり、このような接着部を増設することによって一対の基板同士の密着性を高めて耐久性を向上させ、色素増感型太陽電池が変形した場合でも一対の基板同士が剥離するのを抑制する効果をもたせた構成となっている。
そのため、封止材同士の間の領域において、フィルム基板の厚さ方向(透明基板と対極基板とが対向する方向)の外寄りが収縮するとともに内寄りが伸長し、電子デバイス全体にわたって変形が生じる。つまり、双方のフィルム基板間の隙間の大きさが、フィルム基板の中央付近で最も小さく、端縁に至るほど隙間が大きくなるように形成される。このため、双方の基板の間に設けられる電解質の厚みが、基板の中央付近と端縁付近とで大きく異なるように変動するので、構成される電子デバイスが色素増感型太陽電池の場合には発電効率が低下する虞がある。
また、前述したような変形が生じると、フィルム基板間のギャップが不均一となり、フィルム基板を見たときに図16に示すように電解質3が模様(図16の符号M)のように見えてしまい、美観などの意匠性が低下することとなり、その点で改善の余地があった。
(1)本発明の一態様に係るフィルム基材を用いた電子デバイスは、透明電極を形成させた透明基板と、対向電極を形成させた対極基板と、前記透明電極上に形成させ多孔質の半導体材料に増感色素を担持させて形成させた半導体層と、前記半導体層と対向電極との間に設けられる液状又は擬液状の電解質と、前記電解質を封止して前記透明基板と前記対極基板とを固着させる封止材と、を備えたフィルム基材を用いた電子デバイスであって、前記透明基板及び前記対極基板は、それぞれ可撓性を有する透明フィルムから形成され、前記封止材同士の間の前記電解質において、前記半導体層と前記対極基板との間にスペーサが挟持されていることを特徴としている。
このように電子デバイス全体にわたって変形がなくなることから、透明基板と対極基板とが接触しなくなるうえ、電解質の厚みが変化するのを小さく抑えることができ、発電効率の低下を抑制することができる。
また、この場合には、電解質の厚みが一定となるので、透明フィルムを介して厚みが不均一な電解質が模様のように見えることがなくなり、意匠性の低下を防止することができる。
さらに、本発明では、半導体層と対極基板との間にスペーサが設けられているので、入射光を散乱させ、再度、半導体電極に戻すことが可能となるので、発電効率の向上を図ることができる。
前記スペーサは、前記加熱ロールの表面温度に対し、0℃から20℃低い範囲で、体積が3%以上熱膨張する特性を有することが好ましい。より好ましくは、5%以上、さらに好ましくは10%以上である。
また、0℃から20℃低い範囲で、体積が25%以下膨張する特性を有することが好ましい。より好ましくは、20%以下、さらに好ましくは15%以下である。
ここで、溶融あるいは軟化し、接着性を発現する材料としては、熱可塑性樹脂あるいは、熱可塑性樹脂を含む樹脂組成物等が挙げられる。
気泡を含有する前記樹脂組成物からなる多孔質体、発泡剤を含む前記樹脂からなる樹脂組成物等を例示できる。
本実施の形態の電子デバイスは、フィルム型の色素増感太陽電池を一例として説明するが、本発明の電子デバイスは色素増感太陽電池に限定されない。図1は、色素増感太陽電池10の概略構成を示す断面図である。
具体的に色素増感太陽電池10は、透明導電膜12(透明電極)を形成させた透明基板11と、対向導電膜22(対向電極)を形成させた対極基板21と、透明導電膜12上に形成させ多孔質の半導体材料に公知の増感色素を担持させて形成させた半導体層13と、半導体層13と対向導電膜22との間に設けられる液状又は擬液状の電解質3と、電解質3を封止して透明基板11と対極基板21とを固着させる封止材41を有する封止機能付導通材4と、を備えている。
半導体層13には、電解質3が接触する多孔質内部を含む表面において、公知の増感色素が吸着している。
対向電極2は、対極基板21と、対極基板21上に積層された対向導電膜22と、対向導電膜22上に積層された触媒層(図示省略)と、を備えている。
スペーサ5は、加熱により熱膨張する材料からなり、熱膨張した状態で透明基板11と対極基板21との間に挟持され固定され、ラミネート前の熱膨張前の状態では熱膨張後よりも小さい形状である。スペーサ5は、例えば、膨張黒鉛、発泡剤が内部に取り込まれたポリスチレンビーズ(熱で発泡し膨張)、等が挙げられ、色素増感太陽電池1を加熱ロール間に通過させるラミネート時の加熱温度で熱膨張する特性を有することが好ましい。
また、スペーサ5は、電解質3の領域に配置されてもよい。電解質3の領域にスペーサ5が配置されることにより、透明基板11と対極基板21の間隔を、一層維持し易くなる。
この場合、スペーサの材質は、電解質によって劣化しにくい材質であることが好ましい。例えば、シリコン系樹脂、フッ素系樹脂等の材料が例示できる。
薄くて軽いフレキシブルな色素増感太陽電池を製造する観点からは、基材はガラス、PETフィルム又はPENフィルムであることがより好ましい。基材がガラスである場合は、厚さが0.5mm以下である場合は、屈曲性を有するため好ましい。さらに好ましい厚さは0.3mm以下である。
封止材41の材料としては、例えば、ホットメルト接着剤(熱可塑性樹脂)、熱硬化性樹脂、紫外線硬化性樹脂、並びに、紫外線硬化性樹脂及び熱硬化性樹脂を含んだ樹脂等、一時的に流動性を有し、適当な処理により固化される樹脂材料等が挙げられる。前記ホットメルト接着剤としては、例えば、ポリオレフィン樹脂、ポリエステル樹脂、ポリアミド樹脂等が挙げられる。前記熱硬化性樹脂としては、例えば、エポキシ樹脂、ベンゾオキサゾン樹脂等が挙げられる。前記紫外線硬化性樹脂としては、例えば、アクリル酸エステル、メタクリル酸エステル等の光重合性のモノマーを含むものが挙げられる。
上述した構成のフィルム基材を用いた色素増感太陽電池10の製造方法としては、図3に示すように、封止材41、41同士の間の電解質3において、半導体層13と対極基板21との間で半導体層13上に熱膨張前のスペーサ5および電解質3を配置する。その後、半導体電極1と対向電極2を重ね合わせた色素増感太陽電池10を図示しない加熱ロール間に通過させてラミネートする。スペーサ5はあらかじめ、電解質3中に分散させていてもよい。
このように色素増感太陽電池10全体にわたって変形がなくなることから、透明基板11と対極基板21とが接触しなくなるうえ、電解質3の厚みが変化するのを小さく抑えることができ、発電効率の低下を抑制することができる。
また、電解質3の厚みが一定となるので、透明フィルムを介して厚みが不均一な電解質が模様のように見えることがなくなり、意匠性の低下を防止することができる。
さらに、本実施の形態では、半導体層13と対極基板21との間にスペーサ5が設けられているので、入射光を散乱させ、再度、半導体電極に戻すことが可能となるので、発電効率の向上を図ることができる。
次に、第2の実施の形態によるフィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法について、図面に基づいて説明する。
図5および図6に示すように、第2の実施の形態によるスペーサ5Aは、対極基板21に固着されるとともに、透明基板11と対極基板21とが対向する方向の内寄りに向けて突出する突起状に形成されている。この突起状のスペーサ5Aは、ラミネート前に予め対極基板21の内面21aに対して柱状に垂設され、断続的に(非連続的に)複数が設けられている。スペーサ5Aの高さ寸法hは、ラミネート後の半導体層13と対極基板21(対向導電膜22)との間の間隔に一致している。スペーサ5Aの断面形状は、円形、角形などに制限されることはない。また、突出方向に沿って断面形状が同じでもよいし、変化していてもよいが、半導体層13に接する突出端は半導体層13に平行な平面であることが好ましい。
なお、第2の実施の形態では、突起状のスペーサ5Aが対極基板21に固着されているが、半導体層13寄りに複数の突起状のスペーサ5Aを設けるようにしてもよい。要は、半導体層13と対極基板21のうち少なくとも一方にスペーサ5Aが固定された構造であればよい。
次に、第3の実施の形態によるフィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法について、図面に基づいて説明する。
図7および図8に示すように、第3の実施の形態による色素増感太陽電池10は、スペーサ5Bが加熱により溶融する材料からなり、表面が溶融した状態で隣接するスペーサ5B、5B同士が結合された構成となっている。スペーサ5Bは、色素増感太陽電池10を加熱ロール間に通過させるラミネート時の加熱温度で表面が溶融または軟化する特性を有している。
本実施の形態のスペーサ5Bは、上述した第1の実施の形態のように熱膨張しない部材であるから、ラミネート前後で大きさはほぼ同等であり、ラミネート後の透明基板11と対極基板21との間に挟持され固定された状態で介在される寸法に設定されている。
スペーサ5Bは、電解質3中に分散させておいてもよい。
また、本実施の形態では、スペーサ5Bが色素増感太陽電池10を加熱ロール間に通過させるラミネート時の加熱温度で表面が溶融する特性を有しているので、ラミネート時の加熱温度に達したときにスペーサ5Bの表面を確実に溶融または軟化させることができる。
次に、第4の実施の形態によるフィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法について、図面に基づいて説明する。
図9に示す第4の実施の形態では、スペーサ5Cが加熱により溶融または軟化する材料からなり、表面が溶融または軟化した状態でスペーサ5Cと対極基板21同士が結合された構成となっている。スペーサ5Cは、色素増感太陽電池10を加熱ロール間に通過させるラミネート時の加熱温度で表面が溶融または軟化する特性を有している。
本実施の形態のスペーサ5Cは、上述した第2の実施の形態と同様の材料を用いることができ、ラミネート前後で大きさはほぼ同等であり、ラミネート後の透明基板11と対極基板21との間に挟持され固定された状態で介在される寸法に設定されている。
また、本実施の形態では、スペーサ5Cが色素増感太陽電池10を加熱ロール間に通過させるラミネート時の加熱温度で表面が溶融または軟化する特性を有しているので、ラミネート時の加熱温度に達したときにスペーサ5Cの表面を確実に溶融させることができる。
次に、第5の実施の形態によるフィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法について、図面に基づいて説明する。
第5の実施の形態は、図10A及び図10Bに示すUV照射装置7を用いた色素増感太陽電池の製造方法である。図11A、図11B、及び図11Cに示すように、スペーサ5Dは、UV照射による熱や光(紫外線)によって発泡(膨張)する特性を有する熱硬化性、又は光硬化性の樹脂材料からなり、上述した第1の実施の形態と同様に膨張した状態で透明基板11と対極基板21との間に挟持されて固定されている。そして、複数のスペーサ5Dは、色素増感太陽電池10の製造工程の一部に有するUV照射工程においてUV照射される前の膨張前の状態では膨張後よりも小さい形状となっている。スペーサ5Dは、封止材41、41同士の間の電解質3において、不規則な位置で、かつ複数が配置されている。なお、図11A~図11Cにおいて、スペーサ5Dは球状をなしているが、球状であることに制限されることはなく、任意の形状で配置することが可能である。
したがって、第5の実施の形態においても色素増感太陽電池10全体にわたって変形がなくなることから、透明基板11と対極基板21とが接触しなくなるうえ、電解質3の厚みが変化するのを小さく抑えることができ、発電効率の低下を抑制することができる。そして、上述した実施の形態と同様に、電解質3の厚みが一定となるので、透明フィルムを介して厚みが不均一な電解質が模様のように見えることがなくなり、意匠性の低下を防止することができる。
第6の実施の形態による色素増感太陽電池10は、図12に示すように、スペーサ5EがUV照射による熱や光(紫外線)によって溶融する特性を有する熱硬化性、又は光硬化性の樹脂材料、或いは粒子からなり、表面が溶融した状態で隣接するスペーサ5E、5E同士が結合された構成となっている。スペーサ5Eは、UV照射後の透明基板11と対極基板21との間に挟持され固定された状態で介在される寸法に設定されている。なお、スペーサ5Eは、電解質3中に分散させておいてもよい。
UV照射装置7によりスペーサ5Eに照射される紫外線の波長は、使用されるスペーサ5Eの樹脂の種類等の条件に応じて適宜設定される。また、その他、UV照射装置7の配置台数は、上述した第5の実施の形態と同様である。
図13に示す第7の実施の形態による色素増感太陽電池10は、図14に示すように、透明導電膜12を形成させた透明基板11上に設けられるとともに、半導体層13の端部に配置され、封止材の延在方向に平行かつ直交(交差)する方向に延びる集電配線44を覆う保護材43が設けられ、この保護材43から対向電極2寄りに向けて突出する突起部43aを設けた構成となっている。この突起部43aは、保護材43の幅方向の一部(中央部)が突出しており、集電配線44の延在方向に沿って形成されている。なお、突起部43aを含む保持材43は、集電配線44の一部である。ここで、半導体層13の厚みと集電配線44を含む保護材43の厚みは略一致しており、突起部43aが半導体層13よりも対極基板21寄りに向けて突出している。
なお、本実施の形態のスペーサ5としては、ラミネートの過程において熱や光(UV)等によって膨張しない単純な粒子(樹脂、無機、あるいは樹脂と無機の複合)が用いられる。また、スペーサ5は、粒子サイズが一定であること、又は加圧によってつぶれる粒子(後述する第8の実施の形態で記載)であることが好ましい。さらに、スペーサ5の特性として、光の有効利用の観点から、無機粒子、又は有機無機複合粒子であることが好ましい。そして、スペーサ5は、電解質3に混合させた状態で使用することが好ましい。
また、集電配線44及び保護材43は、例えばスクリーン印刷や転写、ディスペンサーを用いた塗布、等の公知の方法により作成することができる。
また、突起部43aは、保護材43の幅方向の一部(中央部)が突出したものに制限されず、保護材43が全幅で突出する構成とすることが好ましい。
なお、上述したように突起部43aが半導体層13よりも対極基板21寄りに向けて突出していればよいことから、集電配線44自体の高さは、半導体層13よりも低くても高くてもかまわない。さらに、本実施の形態では、保護材43と半導体層13とが接しているが、隙間が形成されていてもよい。
図15Aおよび図15Bに示す第8の実施の形態による色素増感太陽電池10の製造方法は、圧力により弾性変形を起こす柔軟性を有する樹脂粒子の材料からなるスペーサ5Fを用いた方法である。
弾性変形する前のスペーサ5Fの径寸法D1(図15A)は、図15Bに示すような製造された最終的な色素増感太陽電池10の透明基板11及び対極基板21との離間D2(ギャップ)よりも大きいものが使用される。
例えば、スペーサ5Fの寸法として、狙いのギャップ(スペーサ5Fを押しつぶしたときの最終的なギャップ)の、3%以上、より好ましくは、5%以上、さらに好ましくは10%以上で、かつ25%以下、より好ましくは、20%以下、さらに好ましくは15%以下である。なお、この寸法範囲よりもサイズが大き過ぎると、弾性変形によりつぶれる際に、上下の基板11、12と接触する面積が大きくなり、発電効率が低下することになる。また、前記寸法範囲よりもサイズが小さ過ぎると、ギャップ保持剤としての機能が低下することになる。
なお、スペーサ5Fの圧縮弾性率は、例えば、柔軟粒子を構成する架橋性単量体と非架橋性単量体との配合比率を調整し、架橋密度を変更する方法や、柔軟性な単量体の配合量を調整する方法などの公知の方法で変更することが可能である。
また、スペーサ5Fの樹脂粒子のCV値(変動係数)は、封止材、導通材に入れる粒子と同等以下のCV値の粒子であることが好ましい。このCV値が周囲の粒子よりも大きい場合には、ギャップが設計値よりも広がってしまい、美観性が低下することになる。なお、CV値は、標準偏差を算術平均で割ることにより算出される。
なお、スペーサ5Fの樹脂粒子を透明基板11と対極基板12との間に配置するタイミングとしては、予めスペーサ5Fの樹脂粒子を電解液に混ぜておき、電解液の充填と同じタイミングとすることが好ましい。
次に、第9の実施の形態によるフィルム基材を用いた電子デバイス、色素増感太陽電池及び電子デバイスの製造方法について説明する。なお、図面としては、上述した第1の実施の形態と同様であることから、図1、図3及び図4を用いて説明する。
第9の実施の形態では、スペーサ5が電解液(符号3)を吸収(吸水)して膨潤する特性を有するゲル状粒子の材料からなる。
このゲル状粒子の膨潤倍率、膨潤の速度は、製造するモジュールのギャップや製造条件によって最適なものを選定すれば良い。そして、膨潤倍率や膨潤速度の調整は、ゲル微粒子を製造する際の架橋剤の添加量を制御し、架橋度を調整する方法や、電解液に使用する溶媒と相互作用を持つ官能基を有するモノマーの配合比を調整する方法などで行うことができる。膨潤率は、高すぎるとゲル状粒子の物理強度が弱くなり、スペーサとして機能を果たさなくなり、低すぎると上下基板の間に挟まる力が弱くなり、移動してしまう。そのため、好ましい倍率としては、体積が3%以上膨張する特性を有することが好ましい。より好ましくは、5%以上、さらに好ましくは10%以上である。体積が25%以下膨張する特性を有することが好ましい。より好ましくは、20%以下、さらに好ましくは15%以下である。
さらに、スペーサの形状は、上述した実施の形態のように球状であることに限定されることはなく、柱状(角柱状、円錐状、円柱状)等のものであってもよい。
2 対向電極
3 電解質
4 封止機能付導電材
5、5A、5B、5C、5D、5E、5F スペーサ
6,6A,6B プレスロール
7 UV照射装置
10 色素増感太陽電池(電子デバイス)
11 透明基板
12 透明導電膜
13 半導体層
21 対極基板
22 対向導電膜
41 封止材
42 導通材
43 保護材
44 集電配線
43a 突起部
Claims (13)
- 透明電極を形成させた透明基板と、
対向電極を形成させた対極基板と、
前記透明電極上に形成させ多孔質の半導体材料に増感色素を担持させて形成させた半導体層と、
前記半導体層と対向電極との間に設けられる液状又は擬液状の電解質と、
前記電解質を封止して前記透明基板と前記対極基板とを固着させる封止材と、を備えたフィルム基材を用いた電子デバイスであって、
前記透明基板及び前記対極基板は、それぞれ可撓性を有する透明フィルムから形成され、
前記封止材同士の間の前記電解質において、前記半導体層と前記対極基板との間にスペーサが挟持されていることを特徴とする、フィルム基材を用いた電子デバイス。 - 前記スペーサは、加熱により熱膨張する材料からなり、熱膨張した状態で前記透明基板と前記対極基板との間に挟持され固定されていることを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、当該電子デバイスを加熱ロール間に通過させるラミネート時の加熱温度で熱膨張する特性を有することを特徴とする、請求項2に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、前記半導体層と前記対極基板のうち少なくとも一方に固着されるとともに、前記透明電極と前記対向電極とが対向する方向の内寄りに向けて突出する突起状に形成されていることを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、加熱により溶融または軟化する材料からなり、表面が溶融または軟化した状態で隣接する前記スペーサ同士、又は前記スペーサと前記基板同士が結合されていることを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、当該電子デバイスを加熱ロール間に通過させるラミネート時の加熱温度で表面が溶融または軟化する特性を有することを特徴とする、請求項5に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、外周に先鋭な突状部が形成され、隣接する前記スペーサ同士が結合され、又は前記スペーサと、一対の前記透明電極および前記対向電極のうち少なくとも一方とが結合されていることを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、UV照射の熱または光により膨張する特性を有することを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、UV照射の熱または光により表面が溶融または軟化する特性を有することを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 前記スペーサは、電解液を吸収して膨潤する特性を有するゲル状粒子の材料からなることを特徴とする、請求項1に記載のフィルム基材を用いた電子デバイス。
- 請求項1乃至10のいずれか1項に記載の電子デバイスを構成していることを特徴とする、色素増感太陽電池。
- 透明電極を形成させた透明基板と、
対向電極を形成させた対極基板と、
前記透明電極上に形成させた多孔質の半導体材料に増感色素を担持させて形成させた半導体層と、
前記半導体層と対向電極との間に設けられる液状又は擬液状の電解質と、
前記電解質を封止して前記透明基板と前記対極基板とを固着させる封止材と、
前記半導体層の端部に配置され、前記封止材の延在方向に平行かつ交差する方向に延びる集電配線と、
を備えたフィルム基材を用いた電子デバイスを構成する色素増感太陽電池であって、
前記透明基板及び前記対極基板は、それぞれ可撓性を有する透明フィルムから形成され、
前記電解質において、前記半導体層と前記対極基板との間にスペーサが挟持され、
前記集電配線の少なくとも一部が、前記集電配線の全長にわたって前記対極基板寄りに向けて前記半導体層よりも突出していることを特徴とする、色素増感太陽電池。 - 請求項1乃至10のいずれか1項に記載の電子デバイスの製造方法であって、
前記封止材同士の間の前記電解質において、前記半導体層と前記対極基板との間にスペーサを配置する工程と、
前記電子デバイスを加熱ロール間に通過させてラミネートする工程と、
を有し、
ラミネート時に、前記スペーサが前記半導体層と前記対極基板との間でそれぞれに挟持されることを特徴とする、電子デバイスの製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001185245A (ja) * | 1999-12-28 | 2001-07-06 | Catalysts & Chem Ind Co Ltd | 光電気セルおよび該光電気セルの半導体膜形成用塗布液 |
JP2004296203A (ja) * | 2003-03-26 | 2004-10-21 | Bridgestone Corp | 色素増感型太陽電池用対向電極及び色素増感型太陽電池 |
JP2005509258A (ja) * | 2001-11-08 | 2005-04-07 | シャルマース テクノロジー ライセンシング アーベー | 光起電素子と製造方法 |
JP2005268107A (ja) * | 2004-03-19 | 2005-09-29 | Mitsubishi Electric Corp | 色素増感型太陽電池とその製造方法 |
JP2013054825A (ja) * | 2011-08-31 | 2013-03-21 | Sekisui Chem Co Ltd | 電気モジュール及び電気モジュールの製造方法 |
JP2013084596A (ja) * | 2011-09-30 | 2013-05-09 | Fujikura Ltd | 色素増感太陽電池 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JP2005509258A (ja) * | 2001-11-08 | 2005-04-07 | シャルマース テクノロジー ライセンシング アーベー | 光起電素子と製造方法 |
JP2004296203A (ja) * | 2003-03-26 | 2004-10-21 | Bridgestone Corp | 色素増感型太陽電池用対向電極及び色素増感型太陽電池 |
JP2005268107A (ja) * | 2004-03-19 | 2005-09-29 | Mitsubishi Electric Corp | 色素増感型太陽電池とその製造方法 |
JP2013054825A (ja) * | 2011-08-31 | 2013-03-21 | Sekisui Chem Co Ltd | 電気モジュール及び電気モジュールの製造方法 |
JP2013084596A (ja) * | 2011-09-30 | 2013-05-09 | Fujikura Ltd | 色素増感太陽電池 |
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